Methods of preparing branched aliphatic alcohols

ABSTRACT

Systems and methods to produced branched aliphatic alcohols are described. Systems may include a dehydrogenation-isomerization unit, an olefin dimerization unit, an olefin isomerization unit, a hydroformylation unit, a dehydrogenation unit, a hydrogenation unit and/or combinations thereof. Methods for producing branched aliphatic alcohols may include isomerization of olefins in a process stream. The isomerized olefins may be hydroformylated to produce aliphatic alcohols. After hydroformylation of the aliphatic alcohols, unreacted components from the hydroformylation process may be separated from the aliphatic alcohols products. The unreacted components from the hydroformylation process may be recycled back into the main process stream or sent to other processing units. Addition of multiple streams to the units may be performed to control reaction conditions in the units.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application Ser.No. 60/511,211 filed Oct. 15, 2003, the entire disclosure of which isherein incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention generally relates to systems and methods forpreparing aliphatic alcohols. More particularly, embodiments describedherein relate to systems and methods for preparing branched aliphaticalcohols.

2. Description of Related Art

Aliphatic alcohols are important compounds that may be used in a varietyof applications or converted to other chemical compounds (e.g.,surfactants, sulfates). Surfactants may be used in a variety ofapplications (e.g., detergents, soaps, oil recovery).

The structural composition of the aliphatic alcohol may influence theproperties of the surfactant and/or detergent (e.g., water solubility,biodegradability and cold water detergency) produced from the aliphaticalcohol. For example, water solubility may be affected by the linearityof the aliphatic portion of the aliphatic alcohol. As the linearity ofthe aliphatic portion increases, the hydrophilicity (i.e., affinity forwater) of the aliphatic alcohol surfactant may decrease. Thus, the watersolubility and/or detergency performance of the aliphatic alcoholsurfactant may decrease. Incorporating branches into the aliphaticportion of the aliphatic alcohol surfactant may increase the cold-watersolubility and/or detergency of the aliphatic alcohol surfactant.Biodegradability, however, of the aliphatic alcohol surfactants may bereduced if the branches in the aliphatic portion of the alcoholsurfactant include a high number of quaternary carbons. Incorporation ofbranches with a minimum number of quaternary carbon atoms into thealiphatic portion of the aliphatic alcohol surfactant may increasecold-water solubility and/or detergency of the alcohol surfactants whilemaintaining the biodegradability properties of the detergents.

The aliphatic portion of an aliphatic alcohol used to manufacture asurfactant may include one or more aliphatic alkyl groups as branches.Aliphatic alkyl groups that may form branches in the aliphatic portionmay include methyl, ethyl, propyl or higher alkyl groups. Quaternary andtertiary carbons may be present when the aliphatic portion is branched.The number of quaternary and tertiary carbons may result from thebranching pattern in the aliphatic portion. As used herein, the phrase“aliphatic quaternary carbon atom” refers to a carbon atom that is notbound to any hydrogen atoms.

U.S. Pat. No. 5,112,519 to Giacobbe et al., entitled “Process forProduction of Biodegradable Surfactants and Compositions Thereof, ”which is incorporated by reference as if fully set forth herein,describes the manufacture of a surfactant by oligomerizing C₃ and C₄olefins.

U.S. Pat. No. 6,222,077 to Singleton et al., entitled “Dimerized AlcoholCompositions and Biodegradable Surfactants Made Therefrom Having ColdWater Detergency”, which is incorporated by reference as if fully setforth herein, describes a process to manufacture linear alcohols bydimerizing an olefin feed comprising C₆-C₁₀ linear olefins to obtainC₁₂-C₂₀ olefins. The dimerized olefins may be converted to alcohols byhydroformylation.

U.S. Pat. No. 5,849,960 to Singleton et al. entitled “Highly BranchedPrimary Alcohol Compositions, and Biodegradable Detergents MadeTherefrom” and U.S. Pat. No. 6,150,322 to Singleton et al., entitled“Highly Branched Primary Alcohol Compositions, and BiodegradableDetergents Made Therefrom,” both of which are incorporated by referenceas if fully set forth herein, describe processes to manufacture branchedprimary alcohol compositions.

SUMMARY

In an embodiment, aliphatic alcohols may be produced by a method thatincludes dehydrogenation of paraffins to olefins and isomerization ofthe olefins in a dehydrogenation-isomerization unit. A process feedstream entering a dehydrogenation-isomerization unit may include linearolefins and paraffins having an average carbon number from 7 to 18. Inan embodiment, a process feed stream entering adehydrogenation-isomerization unit includes linear olefins and paraffinshaving an average carbon number from 10 to 17. As used herein, thephrase “carbon number” refers to the total number of carbon atoms in amolecule. The process feed stream entering adehydrogenation-isomerization unit, in some embodiments, is derived froma Fischer-Tropsch process.

At least a portion of the paraffins in the feed stream may bedehydrogenated to form olefins in the dehydrogenation-isomerizationunit. At least a portion of the resulting olefins and at least a portionof the olefins that were already present in the feed stream may also beisomerized in the dehydrogenation-isomerization unit. An isomerizationprocess converts linear olefins (e.g., unbranched olefins) into branchedolefins. The isomerized olefins may be hydroformylated to producealiphatic alcohols. After hydroformylation of the olefins, unreactedcomponents from the hydroformylation process may be separated from thealiphatic alcohol products. Paraffins and unreacted olefins in theseparated stream may be recycled back into thedehydrogenation-isomerization unit.

Process conditions in the dehydrogenation-isomerization unit may be suchthat the resulting branched olefins have an average number of branchesper olefin molecule from about 0.7 to about 2.5. The branched olefinsmay include, but are not limited to, methyl and/or ethyl branchedolefins. The isomerization process may produce branched olefins thatinclude less than 0.5 percent of quaternary aliphatic carbon atoms. Thedehydrogenation-isomerization unit may include a catalyst that has twofunctions, to dehydrogenate the paraffins to olefins and to isomerizethe olefins into branched olefins.

In an embodiment, a dehydrogenation-isomerization unit may include aplurality of zones. The plurality of zones may include a first reactionzone and a second reaction zone. The first reaction zone may be adehydrogenation zone. The second reaction zone may be an isomerizationzone. A hydrocarbon stream, containing olefins and paraffins, may enterthe dehydrogenation zone. At least a portion of the paraffins in thehydrocarbon stream may be dehydrogenated to olefins to produce a streamenriched in olefins. The enriched olefin stream may be passed into theisomerization zone. In the isomerization zone, at least a portion of theolefins in the enriched olefin stream may be isomerized to branchedolefins. The branched olefins may be converted to aliphatic alcohols byhydroformylation. After hydroformylation of the olefins, a paraffins andunreacted olefins stream may be separated from the produced aliphaticalcohol products. The paraffins and unreacted olefins stream may berecycled by directing at least a portion of the paraffins and unreactedolefins stream back into the dehydrogenation-isomerization unit and/orinto a stream entering the dehydrogenation-isomerization unit.

In certain embodiments, a feed stream is fed into a dimerization unitthat produces dimerized olefins. The produced dimerized olefins mayinclude branched dimerized olefins. A process feed stream entering adimerization unit is derived, in some embodiments, from aFischer-Tropsch process. In an embodiment, produced dimerized olefinsmay be separated from the unreacted components after leaving thedimerization unit. The unreacted components, in some embodiments, may berecycled back into the dimerization unit. The produced dimerized olefinsmay be converted to aliphatic alcohols. In some embodiments, dimerizedolefins may be hydroformylated to produce aliphatic alcohols. Afterhydroformylation of the dimerized olefins, at least a portion ofunreacted components from the hydroformylation process may be separatedfrom the produced aliphatic alcohol products.

At least a portion of the unreacted components and the produceddimerized olefins may be separated to produce an unreacted hydrocarbonstream and a produced dimerized olefins stream. At least a portion ofthe unreacted hydrocarbon stream may be recycled to the dimerizationunit.

Process conditions in the dimerization unit may be such that theresulting branched olefins have an average number of branches per olefinmolecule from about 0.7 to about 2.5. The branched olefins may include,but are not limited to, methyl and/or ethyl branched olefins. Adimerization unit may produce branched olefins that include less than0.5 percent of quaternary carbon atoms. In an embodiment, a feed streamentering the dimerization unit includes alpha-olefins having an averagecarbon number from 4 to 9. The branched olefins produced from thedimerization of alpha-olefins having an average carbon number from 4 to9 will have an average carbon number from 8 to 18.

In an embodiment, an isomerization unit may be used to produce branchedolefins. In an embodiment, at least a portion of the product streamexiting a dimerization unit may be combined with at least a portion ofthe product stream exiting an isomerization unit and the combined streamdirected to a hydroformylation unit. At least a portion of the olefinsin the combined stream may be hydroformylated in the hydroformylationunit to produce aliphatic alcohols. After hydroformylation of theolefins, at least a portion of unreacted components from thehydroformylation process may be separated from the aliphatic alcoholproducts. At least a portion of the unreacted components may beseparated.

Isomerization of olefins in a process stream may occur in anisomerization unit. In certain embodiments, a process feed streamentering an isomerization unit is derived from a Fischer-Tropschprocess. At least a portion of the linear olefins in a process feedstream may be isomerized to branched olefins in the isomerization unit.The resulting branched olefins may have an average number of branchesper olefin molecule from about 0.7 to about 2.5. The branched olefinsmay include, but are not limited to, methyl and/or ethyl branchedolefins. The isomerization process may produce branched olefins thatinclude less than 0.5 percent of aliphatic quaternary carbon atoms.

In an embodiment, one or more hydrocarbon streams may be combined withthe feed stream entering an isomerization unit. The hydrocarbon streammay be mixed with the feed stream to alter the concentration of theolefins entering the isomerization unit. After the feed stream isprocessed in the isomerization unit, the resulting branchedolefin-containing stream is passed into a hydroformylation unit. One ormore hydrocarbon streams may be combined with the branchedolefin-containing stream to alter the concentration of olefins enteringthe hydroformylation unit. After hydroformylation of the olefins,unreacted components from the hydroformylation process may be separatedfrom the aliphatic alcohol products. Paraffins and unreacted olefins inthe separated stream may be sent to a dehydrogenation unit.

Dehydrogenation of paraffins may occur in a dehydrogenation unit. In anembodiment, at least a portion of a paraffins and unreacted olefinsstream may enter a dehydrogenation unit. In the dehydrogenation unit, atleast a portion of the paraffins in the paraffins and unreacted olefinsstream may be dehydrogenated to produce olefins. At least a portion ofthe produced olefins may exit the dehydrogenation unit to form anolefinic hydrocarbon stream. The resulting olefinic hydrocarbon streamfrom the dehydrogenation process may be recycled back into theisomerization unit and/or into a stream entering the isomerization unit.

In an embodiment, a feed stream containing olefins and paraffins may beprocessed in a hydrogenation unit. A process feed stream entering ahydrogenation unit is derived, in some embodiments, from aFischer-Tropsch process. In the hydrogenation unit at least a portion ofthe olefins in the feed stream may be hydrogenated to form paraffins.The resulting paraffinic feed stream may be fed into a dehydrogenationunit. At least a portion of the paraffins may be dehydrogenated to forman olefinic hydrocarbons feed stream. The resulting olefinic hydrocarbonstream from the dehydrogenation process may be introduced into adimerization unit and/or an isomerization unit. At least a portion ofthe resulting olefins may be hydroformylated to produce aliphaticalcohols.

In an embodiment, a feed stream containing olefins and paraffins may beprocessed in a hydrogenation unit. A process feed stream entering ahydrogenation unit is derived, in some embodiments from aFischer-Tropsch process. In the hydrogenation unit at least a portion ofthe olefins in the feed stream may be hydrogenated to form paraffins.The resulting paraffinic feed stream may be fed into adehydrogenation-isomerization unit. At least a portion of the paraffinsin the feed stream may be dehydrogenated to form olefins. Thedehydrogenation-isomerization unit may also isomerize at least a portionof the resulting olefins and at least a portion of the olefins that werealready present in the feed stream. The olefins produced from thedehydrogenation-isomerization unit may be hydroformylated to producealiphatic alcohols. At least a portion of the aliphatic alcohols mayhave a branched aliphatic structure.

In certain embodiments, at least a portion of the aliphatic alcohols maybe sulfated to form aliphatic sulfates. In some embodiments, aliphaticsulfates may include branched alkyl groups.

In certain embodiments, at least a portion of the produced aliphaticalcohols may be oxyalkylated to form oxyalkyl alcohols. In someembodiments, oxyalkyl alcohols may include branched alkyl groups. Insome embodiments, at least a portion of the produced branched aliphaticalcohols may be ethoxylated to form branched ethoxyalkyl alcohols. Atleast a portion of the oxyalkyl alcohols may be sulfated to fromoxyalkyl sulfates. In some embodiments, oxyalkyl sulfates may includebranched alkyl groups.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of the present invention will become apparent to thoseskilled in the art with the benefit of the following detaileddescription of embodiments and upon reference to the accompanyingdrawings, in which:

FIG. 1 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using adehydrogenation-isomerization unit.

FIG. 2 illustrates structures of aliphatic and olefin sites asdetermined by ¹H NMR analysis in an embodiment of a method to producebranched aliphatic alcohols.

FIG. 3 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using adehydrogenation-isomerization unit and a separation unit to separatebranched olefins from linear olefins and paraffins.

FIG. 4 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using adehydrogenation-isomerization unit with addition of an additionalhydrocarbon stream.

FIGS. 5 A-B depict schematic diagrams of embodiments of a system forproducing branched aliphatic alcohols using a two-zonedehydrogenation-isomerization unit.

FIG. 6 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using adehydrogenation-isomerization unit with a stacked bed catalystconfiguration.

FIG. 7 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using a dimerization unit.

FIG. 8 depicts a schematic diagram of an embodiment of a separation unitto separate produced dimerized olefins from a reaction mixture.

FIG. 9 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using a dimerization unit and anisomerization unit.

FIG. 10 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using an olefin isomerizationunit.

FIG. 11 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using a isomerization unit and aseparation unit to separate branched olefins from linear olefins andparaffins.

FIG. 12 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using an olefin isomerization unitwith addition of an additional hydrocarbon stream.

FIG. 13 depicts a schematic diagram of an embodiment of a system forproducing aliphatic alcohols using a hydrogenation unit and adehydrogenation-isomerization unit.

FIG. 14 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using a hydrogenation unit, adehydrogenation-isomerization unit and a separation unit to separatebranched olefins from linear olefins and paraffins.

FIG. 15 depicts a schematic diagram of an embodiment of a system forproducing aliphatic alcohols using a hydrogenation unit, adehydrogenation unit and a dimerization unit.

FIG. 16 depicts a schematic diagram of an embodiment of a separationunit to separate produced dimerized olefins from a reaction mixture.

FIG. 17 depicts a schematic diagram of an embodiment of a system forproducing aliphatic alcohols using a hydrogenation unit, adehydrogenation unit, a dimerization unit and an isomerization unit.

FIG. 18 depicts a schematic diagram of an embodiment of a system forproducing aliphatic alcohols using a hydrogenation unit, adehydrogenation unit and an isomerization unit.

FIG. 19 depicts a schematic diagram of an embodiment of a system forproducing branched aliphatic alcohols using a hydrogenation unit, adehydrogenation-isomerization unit and a separation unit to separatebranched olefins from linear olefins and paraffins.

While the invention is susceptible to various modifications andalternative forms, specific embodiments thereof are shown by way ofexample in the drawing and will herein be described in detail. It shouldbe understood that the drawings and detailed description thereto are notintended to limit the invention to the particular form disclosed, but onthe contrary, the intention is to cover all modifications, equivalents,and alternatives falling within the spirit and scope of the presentinvention as defined by the appended claims.

DETAILED DESCRIPTION

Hydrocarbon products may be synthesized from synthesis gas (i.e., amixture of hydrogen and carbon monoxide) using a Fischer-Tropschprocess. Synthesis gas may be derived by partial combustion of petroleum(e.g., coal, hydrocarbons), by reforming of natural gas or by partialoxidation of natural gas. The Fischer-Tropsch process catalyticallyconverts synthesis gas into a mixture of products that includessaturated hydrocarbons, unsaturated hydrocarbons and a minor amount ofoxygen-containing products. The products from a Fischer-Tropsch processmay be used for the production of fuels (e.g., gasoline, diesel oil),lubricating oils and waxes.

Fischer-Tropsch process streams may also be used to prepare commodityproducts, which have economic value. For example, linear olefins arecommodity products that are useful for the production of surfactants.Using a portion of the process stream to produce linear olefins mayincrease the economic value of a Fischer-Tropsch process stream.

Surfactants derived from branched olefins may have different propertiesthan surfactants derived from linear olefins. For example, surfactantsderived from branched olefins may have increased water solubility and/orimproved detergency properties compared to surfactants derived fromlinear olefins. Biodegradable properties of the surfactant, however, maybe affected by the presence of quaternary carbon atoms in the branchedportion of the surfactant. Surfactants made from branched olefins with aminimum number of quaternary carbon atoms may have similar biodegradableproperties to surfactants derived from linear olefins. Production ofbranched olefins from a Fischer-Tropsch process stream may increase theeconomic value of the stream. In some embodiments, linear olefins may beconverted into branched olefins with a minimum number of quaternarycarbon atoms using an isomerization catalyst. Increasing the amount ofbranched olefins derived from a Fischer-Tropsch process stream mayincrease the economic value of the process streams.

Methods are described for increasing the amount of branched olefinsderived from a process stream that includes certain amount of olefins,thus increasing the economic value of the process stream. Such methodsare useful for both Fischer-Tropsch process streams and product streamsfrom other sources that include hydrocarbons.

A hydrocarbon feed stream composition may include paraffins and olefins.At least a portion of the hydrocarbon stream may be made up of linearparaffins and olefins having at least 4 carbon atoms and up to 18 carbonatoms. A hydrocarbon feed stream may be obtained from a Fischer-Tropschprocess or from an ethylene oligomerization process. Fischer-Tropschcatalysts and reaction conditions may be selected to provide aparticular mix of products in the reaction product stream. For example,a Fischer-Tropsch catalyst and reaction conditions may be selected toincrease the amount of olefins and decrease the amount of paraffins andoxygenates in the stream. Alternatively, the catalyst and reactionconditions may be selected to increase the amount of paraffins anddecrease the amount of olefins and oxygenates in the stream.

The catalyst used in a Fischer-Tropsch process may be Mo, W, Group VIIIcompounds or combinations thereof. Group VIII compounds include, but arenot limited to, iron, cobalt, ruthenium, rhodium, platinum, palladium,iridium and osmium. Combinations of Mo, W and Group VIII compounds maybe prepared in the free metal form. In an embodiment, combinations ofMo, W and Group VIII compounds may be formed as alloys. Combinations ofMo, W and Group VIII compounds may be formed, in some embodiments, asoxides, carbides or other compounds. In other embodiments, combinationsof Mo, W and Group VIII compounds may be formed as salts. Iron based andcobalt based catalysts have been used commercially as Fischer-Tropschcatalysts. Ruthenium catalysts tend to favor the formation of highmelting waxy species under high-pressure conditions. SyntheticFischer-Tropsch catalysts may include fused iron. In some embodiments, afused iron Fischer-Tropsch catalyst may include a promoter (e.g.,potassium or oxides on a silica support, alumina support orsilica-alumina support). Cobalt metal may also be used in aFischer-Tropsch catalyst. With the proper selection of supports,promoters and other metal combinations, a cobalt catalyst may be tunedto manufacture a composition enriched in the desired hydrocarbonspecies. Other catalysts, such as iron-cobalt alloy catalysts, are knownfor their selectivity toward the production of olefins. Catalysts andcombinations for manufacture of hydrocarbon species by a Fischer-Tropschprocess are generally known.

While reference is made to a Fischer-Tropsch stream, any stream ofolefins and saturated hydrocarbons may be suitable. Many Fischer-Tropschstreams may contain from 5 percent to 80 percent olefins, the remainderbeing saturated hydrocarbons comprising paraffins and other compounds.The Fischer-Tropsch stream may be separated into several streams. Forexample, one stream may include hydrocarbons with an average carbonnumber from 4 to 9 for streams used in a dimerization unit. A secondstream may include hydrocarbons with an average carbon number from 7 to18 for processes that involve an isomerization unit.

In some embodiments, feed streams containing olefins and paraffins areobtained through cracking of paraffin wax or the oligomerization ofolefins. Commercial olefin products manufactured by ethyleneoligomerization are marketed in the United States by Chevron PhillipsChemical Company, Shell Chemical Company (as NEODENE®) and by BritishPetroleum. Cracking of paraffin wax to produce alpha-olefin and paraffinfeed streams is described in U.S. Pat. No. 4,579,986 to Sie, entitled“Process For The Preparation Of Hydrocarbons” and U.S. patentapplication Ser. No. 10/153,955 of Ansorge et al., entitled “Process ForThe Preparation of linear Olefins and Use Thereof To Prepare LinearAlcohols,” both of which are incorporated by reference herein. Specificprocedures for preparing linear olefins from ethylene are described inU.S. Pat. No. 3,676,523 to Mason, entitled “Alpha-Olefin Production;”U.S. Pat. No. 3,686,351 to Mason, entitled “Alpha-Olefin Production;”U.S. Pat. No. 3,737,475 to Mason, entitled “Alpha-Olefin Production” andU.S. Pat. No. 4,020,121 to Kister et al., entitled “OligomerizationReaction System,” all of which are incorporated herein by reference.Most of the above-mentioned processes produce alpha-olefins. Higherlinear internal olefins may be commercially produced (e.g.,chlorination-dehydrochlorination of paraffins, paraffin dehydrogenation,isomerization of alpha-olefins).

In an embodiment, a feed stream is processed to produce a hydrocarbonstream that includes branched olefins. These branched olefins may beconverted to branched aliphatic alcohols using various techniques. Thefeed stream may have a paraffin content range between about 50 percentby weight to about 90 percent by weight of the feed stream. In certainembodiments, a feed stream may have a paraffin content greater than 90percent by weight paraffins. The feed stream may also include olefins.The olefin content of the feed stream may be between about 10 percent byweight to about 50 percent by weight. In other embodiments, a feedstream may have an olefin content greater than 90 percent by weightolefins.

The composition of the feed stream may include hydrocarbons having anaverage carbon number ranging from 4 to 30. In an embodiment, an averagecarbon number of the hydrocarbons in a feed stream may range from 4 to24. In other embodiments, an average carbon number of the feed streammay range from 4 to 18. An average carbon number of the hydrocarbons ina feed stream may range from 7 to 18 for processes that involve anisomerization unit or a dehydrogenation-isomerization unit. In certainembodiments, an average carbon number of the hydrocarbons in a feedstream may range from 10 to 17 for processes that involve anisomerization unit or a dehydrogenation-isomerization unit. In someembodiments, an average carbon number of hydrocarbons in a feed streammay range from 10 to 13 for processes that involve an isomerization unitor a dehydrogenation-isomerization unit. In other embodiments, anaverage carbon number of hydrocarbons in a feed stream may range from 14to 17 for processes that involve an isomerization unit or adehydrogenation-isomerization unit.

The average carbon number of the hydrocarbons in a feed stream may rangefrom 4 to 9 for processes that use a dimerization unit. In certainembodiments, an average carbon number of the hydrocarbons in a feedstream ranges from 5 to 8 for processes that use a dimerization unit. Insome embodiments, an average carbon number of hydrocarbons in a feedstream may range from 5 to 7. In other embodiments, an average carbonnumber of hydrocarbons in a feed stream may range from 7 to 9. A feedstream may include minor amounts of hydrocarbons having a carbon numberthat is higher or lower than the desired carbon number range. In someembodiments, a feed stream may be derived from distillation of a processstream that includes a broader range of carbon numbers.

In an embodiment, a feed stream for a dimerization unit and/or anisomerization unit includes mono-olefins and/or paraffins. Themono-olefins may be of a linear or branched structure. The mono-olefinsmay have an alpha or internal double bond position. The feed stream mayinclude olefins in which 50 percent or more of the olefin moleculespresent may be alpha-olefins of a linear (straight chain) carbonskeletal structure. In certain embodiments, at least about 70 percent ofthe olefins are alpha-olefins of a linear carbon skeletal structure. Ahydrocarbon stream in which greater than 70 percent of all of the olefinmolecules are alpha-olefins of a linear carbon skeletal structure may beused in certain embodiments to convert olefins to aliphatic alcohols.Such a stream may be derived from a Fischer-Tropsch process. In someembodiments, a feed stream includes olefins in which at least about 50percent of the olefin molecules present are internal olefins.

Branched chain olefins may be converted to branched aliphatic alcohols(e.g., branched primary alcohols) by a hydroformylation process.“Hydroformylation,” as used herein, refers to the production of alcoholsfrom olefins via a carbonylation and a hydrogenation process. Otherprocesses may be used to produce aliphatic alcohols from olefins.Examples of other processes to produce aliphatic alcohols from olefinsinclude, but are not limited to, hydradration, oxidation and hydrolysis,sulfation and hydration, and epoxidation and hydration. The compositionof an alcohol product stream may include aliphatic alcohols having anaverage carbon number ranging from 5 to 31. In an embodiment, an averagecarbon number of the aliphatic alcohols in an alcohol product stream mayrange from 7 to 19. In certain embodiments, an average carbon number ofthe aliphatic alcohols in an alcohol product stream may range from 11 to18. In some embodiments, an average carbon number of aliphatic alcoholsin an alcohol product stream may range from 11 to 14 for processes thatinvolve an isomerization unit or a dehydrogenation-isomerization unit.In other embodiments, an average carbon number of aliphatic alcohols inan alcohol product stream may range from 15 to 18 for processes thatinvolve an isomerization unit or a dehydrogenation-isomerization unit.

For processes that involve a dimerization unit, an average carbon numberof aliphatic alcohols in an alcohol product stream may range from 9 to19. In certain embodiments that involve a dimerization unit, an averagecarbon number of aliphatic alcohols in an alcohol product stream mayrange from 11 to 17. In some embodiments that involve a dimerizationunit, an average carbon number of aliphatic alcohols in an alcoholproduct stream may range from 11 to 15. In other embodiments thatinvolve a dimerization unit, an average carbon number of aliphaticalcohols in an alcohol product stream may range from 15 to 19.

In certain embodiments, a first hydrocarbon stream that includesparaffins and olefins may be introduced into adehydrogenation-isomerization unit. The dehydrogenation-isomerizationunit may replace two independent units (e.g., an isomerization unit anda dehydrogenation unit). The dehydrogenation-isomerization unit maydehydrogenate paraffins to olefins and isomerize the resulting olefinsand/or initial olefins present in the hydrocarbon stream to branchedolefins. In an embodiment, a catalyst may perform thedehydrogenation-isomerization of the hydrocarbons in the firsthydrocarbon stream. In certain embodiments, a catalyst may be a singlecatalyst. The catalyst, in some embodiments, may be a mixture of twocatalysts (e.g., a dehydrogenation catalyst and an isomerizationcatalyst). In other embodiments, two separate catalysts located indifferent zones or in a stacked bed configuration in onedehydrogenation-isomerization unit may perform thedehydrogenation-isomerization process. As used herein, “adehydrogenation-isomerization catalyst” may be one or more catalysts.

In certain embodiments, a dehydrogenation-isomerization unit may haveseveral points of entry to accommodate different process streams. Theprocess streams may be from other processing units and/or storage units.Examples of process streams include, but are not limited to, a diluenthydrocarbon stream, and/or other hydrocarbon streams that includeolefins and paraffins derived from other processes. As used herein,“entry into the dehydrogenation-isomerization unit” refers to entry ofprocess streams into the dehydrogenation-isomerization unit through oneor more entry points.

A first hydrocarbon stream, including a mixture of olefins andparaffins, may be introduced into dehydrogenation-isomerization unit 110via first conduit 112 as depicted for System 100 in FIG. 1. Hydrocarbonsin the first hydrocarbon stream may have an average carbon number from 7to 18. In certain embodiments, hydrocarbons in the first hydrocarbonstream may have an average carbon number from 10 to 17. In someembodiments, hydrocarbons in the first hydrocarbon stream may have anaverage carbon number from 10 to 13. In other embodiments, hydrocarbonsin the first hydrocarbon stream may have an average carbon number from14 to 17. In some embodiments, a first hydrocarbon stream includesalpha-olefins. The alpha-olefin content of the first hydrocarbon streammay be greater than 70 percent of the total amount of olefins in thefirst hydrocarbon stream. In certain embodiments, a first hydrocarbonstream may be produced from a Fischer-Tropsch process.

In dehydrogenation-isomerization unit 110, at least a portion of theparaffins in the first hydrocarbon stream may be dehydrogenated toolefins. At least a portion of the resulting olefins and at least aportion of the olefins that were already present in the feed stream maybe isomerized to produce a second hydrocarbon stream. The isomerizationprocess converts linear olefins (i.e., unbranched olefins) into branchedolefins.

The catalyst used for the dehydrogenation-isomerization of the firsthydrocarbon stream may be based on a zeolite catalyst modified with oneor more metals or metal compounds. The catalyst used indehydrogenation-isomerization unit 110 to treat the olefins in the firsthydrocarbon stream may be effective for skeletally isomerizing linearolefins in the process stream into olefins having an average number ofbranches per olefin molecule chain greater than 0.7. In certainembodiments, an average number of branches per olefin molecule chain mayrange from about 0.7 to about 2.5. In some embodiments, an averagenumber of branches per olefin molecule chain may range from about 0.7 toabout 2.2. In other embodiments, an average number of branches perolefin molecule chain may range from about 1.0 to about 2.2.

The dehydrogenation-isomerization catalyst may contain a zeolite havingat least one channel with a crystallographic free channel diametergreater than 4.2 Å and less than 7 Å, measured at room temperature. Asused herein, “channel diameter or size” refers to an effective channeldiameter or size for diffusion. The zeolite may have no channels presentthat have a free channel diameter greater than 7 Å. The catalyst maycontain at least one channel having a crystallographic free diameter atthe entrance of the channel greater than 4.2 Å and less than 7 Å. Thecatalyst may not have a channel with a diameter at the entrance, whichexceeds the 7 Å upper limit of the range. Zeolites possessing channeldiameters greater than 7 Å may be susceptible to undesirable olefinby-products (e.g., aromatization, oligomerization, alkylation, coking).In some embodiments, a zeolite may not contain a channel having a freediameter along either of the x or y planes of greater than 4.2 Å. Asmall channel size may prevent diffusion of the olefin into and/or outof the channel pore once the olefin becomes branched. A zeolite may haveat least one channel with a free diameter of the channel within a rangeof greater than 4.2 Å and less than 7 Å.

In an embodiment, an olefin molecule, due to its high carbon chainlength, may not have to enter into the zeolite channel, diffuse through,and exit the other end of the channel. The rate of branching seen whenpassing the olefin across the zeolite may not correspond to thetheoretical rate of branching if each olefin molecule were to passthrough the channels. Most of the olefins may partially penetrate thechannel for a distance effective to branch the portion of the chainwithin the channel and subsequently withdraw from the channel onceisomerized. In an embodiment of a method to produce aliphatic alcohols,olefin molecules in a hydrocarbon stream may predominately have astructure which is branched at the ends of the olefin carbon backbone,and substantially linear towards the center of the molecule, (e.g., atleast 25 percent of the carbons at the center are unbranched).

In certain embodiments, a zeolite catalyst structure may containchannels having free diameters greater than 4.2 Å and less than 7 Åalong both the x and y planes in the [001] view. Zeolites with thespecified channel size may be referred to as medium or intermediatechannel zeolites and typically have a 10-T member (or puckered 12-Tmember) ring channel structure in one view and a 9-T member or less(small pore) in another view, if any. There is no limit to channelnumbers or orientation (e.g., parallel, non-interconnectingintersections, or interconnecting at any angle) in the zeolite.

Examples of zeolites with a channel size from about 4.2 Å to 7.0 Åinclude molecular sieves, ferrierite, A1PO-31, SAPO-11, SAPO-31,SAPO-41, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48,ZSM-50, ZSM-57, SUZ-4A, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11,MeAPSO-31, and MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41,ELAPSO-11, ELAPSO-31, and ELAPSO-41, laumontite, cancrinite, offretite,hydrogen form of stilbite, the magnesium or calcium form of mordeniteand partheite. The isotypic structures of the zeolite frameworks, knownunder other names, may be considered equivalent. Zeolite framework isdescribed by Flanigen et al.; in “Aluminophosphate Molecular Sieves andthe Periodic Table,” New Developments in Zeolite Science Technology,1986, Kodansha Ltd., Tokyo, Japan, which is incorporated by referenceherein.

Many natural zeolites such as ferrierite, heulandite and stilbite mayfeature a one-dimensional pore structure with a pore size at or slightlysmaller than about 4.2 Å in diameter. U.S. Pat. No. 4,795,623 to Evans,entitled “Time Effective Method For Preparing Ferrierite” and U.S. Pat.No. 4,942,027 to Evans, entitled “Method for Preparing Ferrierite,” bothof which are incorporated by reference herein, describe convertingchannels in natural zeolites to larger channels. Channels in naturalzeolites may be converted to zeolites with desired larger channel sizesby removing an associated alkali metal or alkaline earth metal bygenerally known methods (e.g., ammonium ion exchange, optionallyfollowed by calcination, to yield a zeolite in substantially a hydrogenform). Replacing the associated alkali or alkaline earth metal with thehydrogen form may enlarge the channel diameter. In some embodiments,natural zeolites (e.g., some forms of mordenite) may have a channel sizegreater than 7 Å. The channel size may be reduced by substituting analkali metal for larger ions (e.g., a larger alkaline earth metal).

In certain embodiments, zeolites may have a ferrierite isotypic (orhomeotypic) framework structure. The prominent structural features offerrierite found by x-ray crystallography may be parallel channels inthe alumino-silicate framework. The parallel channels may have anelliptical cross section. Zeolites having a ferrierite isotypicframework structure are described in European Patent No. 55 529 toSeddon et al., entitled, “Zeolites;” and European Patent No. 103 981 toWhittam, entitled “Zeolites.” Zeolites having a ferrierite isotypicframework are also described in U.S. Pat. No. 4,016,245 to Plank et al.,U.S. Pat. No. 4,578,259 to Morimoto et al., entitled “Process ForPreparing A Crystalline Aluminosilicate;” entitled “Crystalline ZeoliteAnd Method Of Preparing Same” and U.S. Pat. No. 4,375,573 to Young etal., entitled “Selective Production And Reaction of P-DisubstitutedAromatics Over Zeolite ZSM-48,” all of which are incorporated byreference as if fully set forth herein.

In an embodiment, a hydrogen form of ferrierite (H-ferrierite) may beconsidered to be substantially one-dimensional. H-ferrierite may haveparallel running channels. H-ferrrierite may have elliptical channelsthat have free diameters of 4.2 Å by 5.4 Å along the x and y planes inthe [001] view. The channels may be large enough to permit entry of alinear olefin and diffusion out of or through the channel of the methylbranched isoolefin. The channels may be small enough to retard cokeformation. Methods for preparing various H-ferrierite are described inU.S. Pat. No. 5,985,238 to Pasquale et al., entitled “Process ForPreparing Ferrierite;” U.S. Pat. No. 4,251,499 to Nanne et al., entitled“Process For The Preparation Of Ferrierite;” U.S. Pat. No. 4,795,623 toEvans, entitled “Time Effective Method For Preparing Ferrierite” andU.S. Pat. No. 4,942,027 to Evans, entitled “Method for PreparingFerrierite;” all of which are incorporated by reference herein.

In certain embodiments, a dehydrogenation-isomerization catalyst may becombined with a refractory oxide that serves as a binder material.Suitable refractory oxides include, but are not limited to, naturalclays (e.g., bentonite, montmorillonite, attapulgite, and kaolin),alumina, silica, silica-alumina, hydrated alumina, titania, zirconia ormixtures thereof.

Examples of alumina binders may include, but are not limited to,pseudoboehmite, gamma and bayerite aluminas. Alumina binders may becommercially available (e.g., LaRoche Chemicals manufactures VERSAL®aluminas and Sasol manufactures CATAPAL® aluminas). In an embodiment,high-dispersity alumina powders may be used as alumina binders whenextrusion is utilized for catalyst preparation. High-dispersity aluminapowders may have a dispersity of greater than 50 percent in an aqueousacid dispersion having an acid content of 0.4-milligram equivalents ofacid (acetic) per gram of powder. Such high-dispersity aluminas may beexemplified by CATAPAL® alumina manufactured by Sasol.

A weight ratio of zeolite to binder material may range from about 10:90to about 99.5:0.5. In some embodiments, a weight ratio may range fromabout 75:25 to about 99:1. In other embodiments, a weight ratio ofzeolite to binder material may range from about 80:20 to about 98:2. Incertain embodiments, a weight ratio of zeolite to binder material mayrange from about 85:15 to about 95:5 on an anhydrous basis.

In certain embodiments, a dehydrogenation-isomerization catalyst may beprepared with one or more monocarboxylic acids and/or inorganic acids.In addition to the monocarboxylic and/or inorganic acids, at least oneorganic acid with at least two carboxylic acid groups (“polycarboxylicacid”) may be used. Monocarboxylic acids may have a substituted orunsubstituted hydrocarbyl group having 1 to 20 carbon atoms. Thehydrocarbyl group may be aliphatic, cyclic or aromatic. Examples ofmonocarboxylic acids having 1 to 20 carbon atoms include, but are notlimited to, acetic acid, formic acid, propionic acid, butyric acid,caproic acid, glycolic acid, lactic acid, hydroxylbutyric acid,hydroxycyclopentanoic acid, salicylic acid, mandelic acid, benzoic acidand fatty acids. Examples of inorganic acids include, but are notlimited to, nitric acid, phosphoric acid, sulfuric acid and hydrochloricacid.

The polycarboxylic acid may, in certain embodiments, be an organic acidwith two or more carboxylic acid groups attached through a carbon-carbonbond linkage to a hydrocarbon segment. The linkage may be at any portionof the hydrocarbon segment. The polycarboxylic acid may have ahydrocarbon segment with less than 10 carbon atoms. The hydrocarbonsegment may be aliphatic, cyclic or aromatic. The hydrocarbon segmentmay have zero carbon atoms for oxalic acid with two carboxylic acidgroups attached through the carbon-carbon bond. Examples of thepolycarboxylic acids include, but are not limited to, tartaric acid,citric acid, malic acid, oxalic acid, adipic acid, malonic acid,galactaric acid, 1,2-cyclopentane dicarboxylic acid, maleic acid,fumaric acid, itaconic acid, phthalic acid, terephthalic acid,phenylmalonic acid, hydroxyphthalic acid, dihydroxyfumaric acid,tricarballylic acid, benzene-1,3,5-tricarboxylic acid, isocitric acid,mucic acid and glucaric acid. The polycarboxylic acids may be anyisomers of the above acids. In some embodiments, the polycarboxylicacids may be any stereoisomers of the above acids. In an embodiment,polycarboxylic acids with at least two carboxylic acid groups and atleast one hydroxyl group are used. In an embodiment, citric acid,tartaric acid and malic acid may be used as polycarboxylic acids.

Metals incorporated into a dehydrogenation-isomerization catalyst may bemetals that promote the oxidation of coke in the presence of oxygen at atemperature greater than 250° C. and the dehydrogenation of paraffins.“Metal(s),” as used herein, refers to metals of a zero oxidation stateand/or higher oxidation states (e.g., metal oxides). As used herein,“coke” refers to a product from thermal degradation of larger moleculesinto smaller molecules.

Metals used in the dehydrogenation-isomerization catalyst may betransition and rare earth metals. Coke oxidation-promoting metalsinclude, but are not limited to, Groups IB, VB, VIIB, VIIB, VIII of thetransition metal series of the Periodic Table and/or combinationsthereof. In certain embodiments, Pd, Pt, Ni, Co, Mn, Ag, Cr and/orcombinations thereof may be used in the dehydrogenation-isomerizationcatalyst. In other embodiments, metal oxides such as, but not limitedto, chrome oxide, iron oxide, noble metals, or mixtures thereof may beused as coke-oxidizing compounds in the catalyst.

An amount of the metal introduced may range from about 5 parts permillion (“ppm”) up to about 15 percent by weight. In certainembodiments, an amount of metal may range from about 5 ppm to about 10percent by weight. In some embodiments, an amount of metal may rangefrom about 5 ppm to about 5 percent by weight.

Noble metals (e.g., platinum and/or palladium) may be used in smalleramounts of metals than other metals incorporated into a zeolite and/orbinder. “Noble metals,” as used herein, refers to metals of the groupthat includes platinum, palladium, iridium, ruthenium, osmium andrhodium. In certain embodiments, an amount of noble metals may rangefrom about 5 ppm to about 2 percent by weight, basis metal, of the finalcatalyst. In some embodiments, an amount of noble metals may range fromabout 5 ppm to about 1000 ppm, basis metal, of the final catalyst. Inother embodiments, an amount of noble metal(s) may range from about 5ppm to about 3000 ppm, basis metal, of the final catalyst. An amount ofnoble metal(s) used in a dehydrogenation-isomerization catalyst may, incertain embodiments, range from about 5 ppm to about 2000 ppm by weight,basis metal, of the final catalyst. An amount of noble metal(s)sufficient to promote regeneration without deteriorating the performanceof the catalyst may be in the range from about 30 ppm to about 100 ppm.Higher amounts of platinum and/or palladium (e.g., greater than 2% byweight) may have an adverse effect on the catalyst (e.g., run life,olefin isomerization activity, selectivity).

In an embodiment, zeolite powder and alumina powder may be mixed (e.g.,mulled) with water and one or more metal compounds of the catalyst. Theresulting mixture may be formed into a pellet. Catalysts prepared bymulling may have superior olefin isomerization performance overcatalysts prepared by impregnation. The term “mulling,” as used herein,refers to mixing of powders to which sufficient water has been added toform a thick paste and wherein the mixing is accompanied by concomitantshearing of the paste. Commercially available mullers such as theLancaster Mix Muller and the Simpson Mix Muller may be used.

The pellet may be formed, in some embodiments, by extrusion. One or morepeptizing acid (e.g., nitric acid, acetic acid, citric acid or mixturesthereof) may be added to the mixture and optional extrusion aids such ascellulose derivatives (e.g., METHOCEL®F4M, hydroxypropylmethylcellulose, manufactured by The Dow Chemical Company) may beutilized. The amounts of peptizing acid used may be determined byroutine experimentation to provide a plastic, extrudable material. Theterm “pellets,” as used herein, refers to any shape or form ofconsolidated materials.

In certain embodiments, a noble metal such as platinum and/or palladiummay be added to the zeolitic catalyst after pelletization. Common metalincorporation methods known to those skilled in the art (e.g.,impregnation, noble metal ion exchange and co-mulling) may be used toproduce a working catalyst useful in dehydrogenation-isomerization ofparaffins. The addition of noble metals to the catalyst may aid in thedehydrogenation reaction of paraffins. Pellets containing noble metalsmay be calcined at a temperature range from about 250° C. to about 700°C. In certain embodiments, a calcination temperature may range fromabout 300° C. to about 600° C. In some embodiments, a calcinationtemperature may range from about 450° C. to about 525° C.

The dehydrogenation-isomerization catalyst may be contacted with thefirst hydrocarbon stream in dehydrogenation-isomerization unit 110 undera variety of conditions to dehydrogenate paraffins to olefins andisomerize the resulting olefins. In dehydrogenation-isomerization unit110, reaction temperatures may range from about 300° C. to about 700° C.A reaction temperature, in some embodiments, may range from about 350°C. to about 550° C. A total pressure of dehydrogenation-isomerizationunit 110 during the reaction may range from about 0.010 atmosphere (1kPa) to about 25.0 atmospheres (2534 kPa). In an embodiment, a totalpressure of dehydrogenation-isomerization unit 110 during the reactionmay range from about 0.010 atmosphere (1 kPa) to about 15.0 atmospheres(1520 kPa). In other embodiments, a total pressure ofdehydrogenation-isomerization unit 110 during the reaction may rangefrom about 1 atmosphere (101 kPa) to about 5.0 atmospheres (507 kPa). Inorder to prevent coking, hydrogen may be fed together with the firsthydrocarbon stream. Hydrogen gas and paraffins present in the firsthydrocarbon stream may be fed at a hydrogen gas to paraffin molar ratioin the range from about 0.1 to about 20. In certain embodiments, ahydrogen gas to paraffin molar ratio may be in the range from about 1 toabout 10.

Residence time in dehydrogenation-isomerization unit 110 may be selectedsuch that conversion level of the paraffins to olefins may be kept below40 mole percent. In an embodiment, a conversion level ranges from 5 molepercent to 30 mole percent. By keeping the conversion level low, sidereactions (e.g., diene formation and cyclization reactions) may beminimized. Olefin conversion may be increased by varying the reactionconditions (e.g., temperature, residence time) as long as side reactionsremain below acceptable limits. Olefins produced indehydrogenation-isomerization unit 110 may have a higher degree ofbranching than a paraffin feed to the dehydrogenation-isomerizationunit. It should be understood that the concentration of olefins producedvia dehydrogenation-isomerization unit 110 may be limited by thethermodynamic equilibrium of olefins and paraffins at the reactiontemperature. The conditions for olefin isomerizationdehydrogenation-isomerization 110 may be controlled such that the numberof carbon atoms in the olefins prior to and subsequent to theisomerization conditions is substantially the same.

Branched olefins produced in dehydrogenation-isomerization unit 110 mayinclude methyl, ethyl and/or longer carbon chain branches. HydrogenNuclear Magnetic Resonance (¹H NMR) analysis of the isomerized olefincomposition may be performed. Branched olefins may include quaternaryand/or tertiary aliphatic carbons. In certain embodiments, an amount ofquaternary aliphatic carbons produced in a unit in which olefinisomerization occurs may be minimized. As used herein, “an unit whereolefin isomerization occurs and/or where branching is introduced in anolefin” refers to a dehydrogenation-isomerization unit, an isomerizationunit and/or a dimerization unit. ¹H NMR analysis of the olefins mayindicate the extent of isomerization of the olefins in the hydrocarbonstream. ¹H NMR analysis may be capable of differentiating a wide rangeof olefin structures such as the olefin structures illustrated in FIG.2.

¹H NMR analysis may use a combination of a 12-degree tip and a 5 secondrecycle delay time. For example, a spectral width of 8 KHz on a 500 MHzinstrument may be used in the analysis. Enough scans (e.g., 64) may beperformed to give adequate signal to noise ratio for the detection ofthe aliphatic and olefinic sites in the olefin molecules. Aliphatic andolefin sites may be calculated through analysis of the resulting ¹H NMRspectrum. It is assumed in the ¹H NMR method one double bond permolecule. The total number of branches is a sum of all aliphatic andolefinic branch sites per olefin molecule. An average carbon number permolecule may be provided as an input to a ¹³C NMR calculation usinggenerally known analytical techniques (e.g., gas chromatography coupledwith mass spectrometry). Aliphatic branches, as used herein, refer tobranches on non-olefinic carbons. Olefinic branches, as used herein,refer to branches on olefinic carbons. The total number of branches on adouble bond may be determined by summation of the individualcontributions of the various assayed olefin units. Olefin units includevinyl, di-substituted, tri-substituted, vinylidene and/ortetra-substituted olefins, as illustrated in FIG. 2. The amount and typeof olefin may vary with process stream composition and isomerizationreaction conditions. In an embodiment, an amount of tetra-substitutedolefin produced may be low.

As illustrated in FIG. 2, vinyl substituted olefin A is defined as anolefin having one functional group (R) and hydrogen H₁ bound to carbonC₂ and two hydrogens H₂ bound to carbon C₁ of the double bond.“Functional group (R)” as used herein, refers to any aliphatic groupother than hydrogen that can be covalently bound to a carbon atom makingup the structure of the double bond. Di-substituted olefin B, as usedherein, refers to an olefin having two functional groups R and twohydrogens H₃ covalently bound to each of the carbon atoms of the doublebond. Olefin B may be a cis-olefin, a trans-olefin or a mixture thereof.Tri-substituted olefin C, as used herein, refer to an olefin havingfunctional groups R and hydrogen H₄ covalently bound to the carbon atomsof the double bond. Vinylidene olefin D, as used herein, refers to anolefin having two functional groups R covalently bound to carbon atom C₂and two hydrogens H₅ covalently bound to carbon atom C₁ of the doublebond. Tetra-substituted olefin E, as used herein, refers to an olefinhaving four functional groups R (i.e., no hydrogens) covalently bound tothe carbons of the double bond. Tetra-substituted olefins are notdirectly detected in the ¹H NMR spectrum since they bear no hydrogensbound to the carbon atoms of the double bond. Tetra-substituted olefinsmay be determined by calculating the difference between the numbers ofall olefin units, as determined from the aliphatic portion of thespectrum adjacent to the double bond (e.g., hydrogens H₆, H₇, and H₈, inStructures F-H) and the directly identified olefins bearing hydrogens oncarbons atoms of the double bond.

For example, in a solution containing olefins A, B, C, D and E, thetotal number of olefin branches per olefin molecule may be calculated inthe following manner. The olefinic branching values may be determined bycalculating the average number of branches of the individualcontributions of the various assayed olefin units. In the solution,vinyl olefin A and di-substituted olefins B (e.g., cis- andtrans-olefins) contribute no olefinic branches. Similarly,tri-substituted olefin C and vinylidene olefin D contribute one olefinbranch each. Tetra-substituted olefin E contributes two olefin branches.Therefore, in this example, the total number of olefinic branches wouldbe four and the average olefin branching per molecule would be about0.67 (4 branches per six olefin molecules).

A total number of branches on aliphatic carbons in the olefin molecules(e.g., structures F and I) may be determined by summation of theindividual contribution of structures with methines adjacent to thedouble bonds (H₆) and structures with methines not adjacent to thedouble bond (H₉). Olefins F and I would each contribute one branch perolefin molecule, assuming no additional aliphatic branches in the Rchains. It is to be understood that, although as shown, olefins F and Iare derivatives of olefin B, methine hydrogens may be found in olefinsA-E depending on the branching in the R groups.

The presence of quaternary carbon atoms may be determined using carbon13 (¹³C) NMR techniques. The type of branching (e.g., methyl, ethyl,propyl or larger groups) may be determined by hydrogenation of theolefin mixture and then ¹³C NMR analysis of the hydrogenated olefinsolution. ¹³C NMR analysis may resolve methyl groups that are directlyattached to the hydrogenated olefin backbone structure (e.g., CH₃ instructure J and K), methyls in ethyl groups attached to the hydrogenatedolefin backbone structure (e.g., CH₃ in structure L), and methyls inpropyl or longer groups attached to the hydrogenated olefin backbonestructure (e.g., CH₃ in structure M). The various methyl peak positionsin FIG. 2 are given in parts per million (ppm) relative to tetramethylsilane.

Methyls in structure M in FIG. 2 may include terminal methyls, propyland/or larger branches. The number of propyl or larger branches may notbe directly obtained from the 13.5-15 ppm peak region in the spectrum.Propyl or larger branched values may be computed by taking thedifference between the total number of branches per molecule and thenumber of methyl and ethyl branches per molecule obtained directly fromthe methyl spectral regions of structures J-L. The total number ofbranches per molecule is determined by adding the number of methyls permolecule and subtracts “two”, wherein “two” accounts for thehydrogenated olefin backbone's terminal methyls.

In an embodiment, an average number of branches per olefin moleculepresent in the produced branched olefin composition may be greater than0.7. In certain embodiments, an average number of branches per olefinmolecule present in the branched olefin composition is from about 0.7 toabout 2.5. In some embodiments, an average number of branches per olefinmolecule present in the branched olefin composition is from about 0.7 toabout 2.2. In certain embodiments, an average number of branches perolefin molecule present in the branched olefin composition is from about1.0 to about 2.2. The degree of branching in the product may becontrolled by controlling process conditions used in a unit in whicholefin isomerization occurs. For example, high reaction temperatures andlower feed rates may result in a higher degree of branching. Methylbranches may represent between about 20 percent to about 99 percent ofthe total number of branches present in the olefin molecules. In someembodiments, methyl branches may represent greater than 50 percent ofthe total number of branches in the olefin molecules. The number ofethyl branches in the olefin molecules may represent, in certainembodiments, less than 30 percent of the total number of branches. Inother embodiments, a number of ethyl branches, if present, may bebetween about 0.1 percent and about 2 percent of the total number ofbranches. Branches other than methyl or ethyl, if present, may be lessthan 10 percent of the total number of branches.

Aliphatic quaternary carbon atoms present in the branched olefincomposition may be less than 2 percent of the carbon atoms present. Inan embodiment, a number of aliphatic quaternary carbon atoms present isless than 1 percent of the carbon atoms present. For applications inwhich biodegradability is important, the number of aliphatic quaternarycarbon atoms may be less than 0.5 percent of the carbon atoms present.In an embodiment, a number of aliphatic quaternary carbon atoms is lessthan 0.3 percent of the carbon atoms present. In other embodiments, anumber of aliphatic quaternary carbon atoms present in the branchedolefin composition is between about 0.01 percent and about 0.3 percentof the aliphatic carbon atoms present.

A second hydrocarbon stream may exit dehydrogenation-isomerization unit110 and be transferred to other processing units (e.g., ahydroformylation unit, separation units, an alkylation units) via secondconduit 114. At least a portion of the second hydrocarbon stream mayexit dehydrogenation-isomerization unit 110 and be introduced intohydroformylation unit 116 via second conduit 114. In hydroformylationunit 116, at least a portion of the olefins in the second hydrocarbonstream may be converted to alcohols. At least a portion of the producedalcohols and at least a portion of the unreacted components of thesecond hydrocarbon stream may form a hydroformylation reaction stream.

In an embodiment, olefins may be separated, if desired, from the secondhydrocarbon stream through techniques generally known in the art (e.g.,distillation, molecular sieves, extraction, adsorption,adsorption/desorption, and/or membranes). Separation of at least aportion of the branched olefins from the linear olefins and paraffinsmay increase the concentration of branched olefins entering thehydroformylation unit. In addition, separation of at least a portion ofthe branched olefins from the linear olefins and paraffins may influencethe ratio of linear to branched olefins produced in the hydroformylationunit.

Referring to FIG. 3, a second hydrocarbon stream may exitdehydrogenation-isomerization unit 110 and enter separation unit 118 viaseparation conduit 120. Separation unit 118 may produce at least twostreams, a branched olefins stream and a linear olefins and paraffinsstream. In separation unit 118, the second hydrocarbon stream may becontacted with organic and/or inorganic molecular sieves (e.g., zeoliteor urea) with the correct pore size for branched olefins and/or linearolefins and paraffins. Subsequent desorption (e.g., solvent desorption)of at least a portion of the branched olefins and/or at least a portionof the linear olefins and paraffins from the molecular sieves mayproduce at least two streams (e.g., a branched olefins stream and alinear olefins and paraffins stream).

Separation unit 118 may include a fixed bed containing adsorbent forseparation of the second hydrocarbon stream to produce a branched olefinand paraffins stream and a linear olefins and paraffins stream.Separation temperatures in separation unit 118 may range from about 100°C. to about 400° C. In some embodiments, separation temperatures mayrange from 180° C. to about 380° C. Separation in separation unit 118may be conducted at a pressure ranging from about 2 atmospheres (202kPa) to about 7 atmospheres (710 kPa). In some embodiments, apretreatment of a second hydrocarbon stream may be performed to preventadsorbent poisoning. An example of an adsorption/desorption process is aMolex process using Sorbex® separations technology (UOP process, UOP,Des Plaines, Ill.). Adsorption/desorption processes are described inU.S. Pat. No. 6,225,518 to Sohn et al., entitled “Olefinic HydrocarbonSeparation Process;” U.S. Pat. No. 5,292,990 to Kantner et al.,entitled, “Zeolite Compositions For Use in Olefinic Separations” andU.S. Pat. No. 5,276,246 to McCulloch et al., entitled “Process ForSeparating Normal Olefins From Non-Normal Olefins,” all of which areincorporated by reference as if fully set forth herein.

At least a portion of the linear olefins and paraffins stream may betransported to other processing units and/or stored on site. In anembodiment, at least a portion of the linear olefins and paraffinsstream may be combined with first hydrocarbon stream in first conduit112 via linear olefin and paraffin recycle conduit 122. The combinedstream may enter dehydrogenation-isomerization unit 110 via firstconduit 112 to continue the process to produce aliphatic alcohols. Insome embodiments, a linear olefins and paraffins stream may beintroduced directly into dehydrogenation-isomerization unit 110.

At least a portion of the branched olefins stream may be transported andutilized in other processing streams and/or stored on site via branchedolefins conduit 124. In some embodiments, at least a portion of abranched olefins stream may exit separation unit 118 and be introducedinto second conduit 114 via branched olefins conduit 124. In otherembodiments, at least a portion of a branched olefins stream may exitseparation unit 118 and be introduced directly into a hydroformylationunit.

Referring to FIG. 1, the second hydrocarbon stream may exitdehydrogenation-isomerization unit and enter hydroformylation unit 116via second conduit 114. Hydroformylation unit 116 may have severalpoints of entry to accommodate entry of additional process streams. Asused herein, “stream entering into the hydroformylation unit” is definedas the entry of process streams into the hydroformylation unit throughone or more entry points. Examples of such process streams include, butare not limited to, additional streams fromdehydrogenation-isomerization unit 110, a diluent hydrocarbon stream,gases and/or other hydrocarbon streams that include olefins andparaffins derived from other processes.

In a hydroformylation process, olefins are converted to aldehydes,alcohols or a combination thereof by reaction of at least a portion ofthe olefins with carbon monoxide and hydrogen according to an Oxoprocess. As used herein, an “Oxo process” refers to the reaction of anolefin with carbon monoxide and hydrogen in the presence of a metalcatalyst (e.g., a cobalt catalyst) to produce an alcohol containing onemore carbon atom than the starting olefin. In other hydroformylationprocesses, a “modified Oxo process” is used. As used herein, a “modifiedOxo process” refers to an Oxo process that uses a phosphine, phosphite,arsine or pyridine ligand modified cobalt or rhodium catalyst.Preparation and use of modified Oxo catalysts are described in U.S. Pat.No. 3,231, 621, to Slaugh, entitled “Reaction Rates In CatalyticHydroformylation”; U.S. Pat. No. 3,239,566 to Slaugh et al., entitled“Hydroformylation Of Olefins;” U.S. Pat. No. 3,239,569 to Slaugh et al.,entitled “Hydroformylation Of Olefins;” U.S. Pat. No. 3,239,570 toSlaugh et al., entitled “Hydroformylation Of Olefins;” U.S. Pat. No.3,239,571 to Slaugh et al., entitled “Hydroformylation Of Olefins;” U.S.Pat. No. 3,400,163 to Mason et al., entitled “Bicyclic Heterocyclic Sec-And Tert-Phosphines;” U.S. Pat. No. 3,420,898 to Van Winkle et al.,entitled “Single Stage Hydroformylation Of Olefins To Alcohols SingleStage Hydroformylation Of Olefins To Alcohols;” U.S. Pat. No. 3,440,291to Van Winkle et al., entitled “Single Stage Hydroformylation Of OlefinsTo Alcohols;” U.S. Pat. No. 3,448,157 to Slaugh et al., entitled“Hydroformylation Of Olefins;” U.S. Pat. No. 3,488,158 to Slaugh et al.,entitled “Hydroformylation Of Olefins;” U.S. Pat. No. 3,496,203 toMorris et al., entitled “Tertiary Organophosphine-Cobalt-CarbonylComplexes;” U.S. Pat. No. 3,496,204 to Morris et al., entitled “TertiaryOrganophosphine-Cobalt-Carbonyl Complexes;” U.S. Pat. No. 3,501,515 toVan Winkle et al., entitled “Bicyclic Heterocyclic TerteriaryPhosphine-Cobalt-Carbonyl Complexes”; U.S. Pat. No. 3,527,818 to Masonet al., entitled “Oxo Alcohols Using Catalysts Comprising DitertiaryPhosphines;” U.S. patent application Ser. No. 10/075,682, entitled “AProcess For Preparing A Branched Olefin, A Method Of Using The BranchedOlefin For Making A Surfactant, and a Surfactant” and in U.S. patentapplication Ser. No. 10/167,209 entitled “Process for the Preparation OfA Highly Linear Alcohol Composition,” all of which are incorporatedherein by reference. Methods of alcohol production are also described byOthmer, in “Encyclopedia of Chemical Technology” 2000, Fourth Edition;and by Wickson, in “Monohydric Alcohols; Manufacture, Applications andChemistry” Ed. Am. Chem. Soc. 1981, both of which are incorporatedherein by reference.

A hydroformylation catalyst used in hydroformylation unit 116 mayinclude a metal from Group VIII of the Periodic Table. Examples ofGroups VIII metals include cobalt, rhodium, nickel, palladium orplatinum. The Group VIII metal may be used as a complex compound. Acomplex compound may be a Group VIII metal combined with a ligand.Examples of ligands include, but are not limited to, a phosphine,phosphite, arsine, stibine or pyridine ligand. Examples ofhydroformylation catalysts include, but are not limited to, cobalthydrocarbonyl catalyst, cobalt-phosphine ligand catalyst,rhodium-phosphine ligand catalyst or combinations thereof.

A source of the Group VIII metal may be a salt. Salts of acids with apKa value from about 2 to about 6 when measured in water at 20° C., maybe used. Examples of suitable acids include nitric acid, sulfuric acid,organic acids and sulfonic acids. Examples of organic acids includeoctanoic acid, dichloroacetic acid, trifluoroacetic acidperfluoropropionic acid and combinations thereof. Examples of sulfonicacids include p-toluenesulfonic acid, benzenesulfonic acid,methanesulfonic acid and combinations thereof.

Ligands of a hydroformylation catalyst may be made of monophosphines. Amonophosphine may include three hydrocarbon groups, three oxy groups, orcombinations of hydrocarbon groups and oxy groups. Monophosphine ligandsmay be attached to arsenic or tin to form a hydroformylation catalyst.Examples of monophosphine ligands include, but are not limited to,triamylphosphine, trihexylphosphine, dimethylethylphosphine,diamylethylphosphine, tricyclopentylphosphine, tricyclohexylphosphine,diphenylbutylphosphine, diphenylbenzylphosphine,diphenyl(2-pyridyl)phosphine, phenyl[bis(2-pyridyl)]phosphine,triethoxyphosphine, butyldiethoxyphosphine, triphenylphosphine,dimethylphenylphosphine, methyldiphenylphosphine,dimethylpropylphosphine, tritoluylphosphine or combinations thereof.

In other embodiments, bidentate phosphine ligands may be used. Bidentatephosphine ligands may be attached to arsenic or antimony to form ahydroformylation catalyst. Examples of bidentate phosphine ligandsinclude, but are not limited to, 1,2-bis(dimethylphosphino)ethane, 1,2-and 1,3-bis(dimethylphosphino)propane, 1,2-bis(diethylphosphino)ethane,1,2-bis [di(1-butyl)phosphino]ethane,1-dimethylphosphino-2-diethylphosphinoethane,1,2-bis(di-phenylphosphino)ethane,1,2-bis(diperfluorophenylphosphino)ethane,1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane,1-dimethylphosphino-2-diphenylphosphinoethane, 1diethylphosphino-3-diphenylphosphinopropane, 1,2-bis[di(o-toluyl)phosphino]ethane or combinations thereof.

In some embodiments, phosphine ligands may includephosphabicyclo-hydrocarbons. Examples of phosphabicyclo-hydrocarbonsinclude, but are not limited, 9-hydrocarbyl-9-phospha-bicyclononane andP,P-bis(9-phosphabicyclononyl)-hydrocarbons in which the smallestP-containing ring contains at least 5 carbon atoms. Examples of ligandsin which the P-containing ring contains at least 5 carbon atoms include,but are not limited to, 9-aryl-9-phosphabicyclo[4.2.1]nonanes;9-(dialkylaryl)-9-phosphabicyclo[4.2.1]nonanes;9-alkyl-9-phospha-bicyclo[4.2.1]nonanes;9-cycloalkyl-9-phospha-bicyclo[4.2.1]nonanes;9-cycloalkenyl-9-phosphabicyclo[4.2.1]nonanes;P,P-bis(9-phosphabicyclo-nonyl)alkanes;9-aryl-9-phosphabicyclo[3.3.1]nonanes;9-(dialkylaryl)-9-phosphabicyclo[3.3.1]nonanes;9-alkyl-9-phospha-bicyclo[3.3.1]nonanes;9-cycloalkyl-9-phospha-bicyclo[3.3.1]nonanes;9-cycloalkenyl-9-phosphabicyclo[3.3.1]nonanes. Other examples of suchligands, include but are not limited to,9-phenyl-9-phosphabicyclo[4.2.1]nonane;9-(2,4-dimethylphenyl)-9-phosphabicyclo[4.2.1]nonane;9-ethyl-9-phosphabicyclo[4.2.1]nonane;9-cyclohexyl-9-phosphabicyclo[4.2.1]nonane;9-cyclopentenyl-9-phospha-bicyclo[4.2.1]nonane;1,2-P,P-bis(9-phosphabicyclo-[4.2.1]nonyl)ethane;1,3-P,P-bis(9-phosphabicyclo-[4.2.1]nonyl)propane;1,4-P,P-bis(9-phosphabicyclo-[4.2.1]nonyl)butane;9-aryl-9-phosphabicyclo[4.2.1]nonanes;9-(dialkylaryl)-9-phosphabicyclo[4.2.1]nonanes;9-alkyl-9-phospha-bicyclo[4.2.1]nonanes;9-cycloalkyl-9-phospha-bicyclo[4.2.1]nonanes;9-cycloalkenyl-9-phosphabicyclo[4.2.1]nonanes;P,P-bis(9-phosphabicyclo-nonyl)alkanes;9-phenyl-9-phosphabicyclo[3.3.1]nonane;9-(2,4-dimethylphenyl)-9-phosphabicyclo[3.3.1]nonane;9-ethyl-9-phosphabicyclo[3.3.1]nonane;9-cyclohexyl-9-phosphabicyclo[3.3.1]nonane;9-cyclopentenyl-9-phospha-bicyclo[3.3.1]nonane;1,2-P,P-bis(9-phosphabicyclo-[3.3.1]nonyl)ethane;1,3-P,P-bis(9-phosphabicyclo-[3.3.1]nonyl)propane;1,4-P,P-bis(9-phosphabicyclo-[3.3.1]nonyl)butane or combinationsthereof.

A phosphine ligand may be used in amounts in a molar ratio of phosphineto metal (e.g., cobalt) in a range from about 0.5 to about 2. In certainembodiments, a molar ratio of alkyl phosphine to metal may be in a rangeof about 0.6 to about 1.8. In addition to the metal and the phosphineligand, the hydroformylation catalyst may also include additionalcomponents for enhancing the stability of the metal/phosphine system. Insome embodiments, a hydroformylation catalyst may include additionalcomponents for improving the alcohol selectivity. Examples of additionalcomponents are potassium hydroxide and sodium hydroxide. The additionalcomponent may be used in a molar ratio of additional component to metalfrom about 0 to about 1.

A source of carbon and hydrogen for a hydroformylation process inhydroformylation unit 116 may be a gas. Examples of gases include, butare not limited to, carbon monoxide, hydrogen or synthesis gas. A ratioof carbon monoxide to hydrogen applied in hydroformylation unit 116 maybe in a range from about 1.0 to about 5.0. In certain embodiments, ahydrogen to carbon monoxide molar ratio may be in a range from about 1.5to about 2.5.

Synthesis gas that contains hydrogen and carbon monoxide in a molarratio from about 1 to about 2.5 may be used in hydroformylation unit116. In other embodiments, synthesis gas that contains hydrogen andcarbon monoxide in a molar ratio from 1.0 to 10.0 may be used. In otherembodiments, synthesis gas that contains a hydrogen and carbon monoxidemolar ratio from 1.5 to 2.5 may be used as a source of carbon andhydrogen. It should be understood that the gas feed may be a mixture ofcarbon monoxide and hydrogen gases only, synthesis gas only orcombinations thereof.

In hydroformylation unit 116, olefins in the second hydrocarbon streammay be hydroformylated using a continuous, semi-continuous or batchprocess. In case of a continuous mode of operation, the liquid hourlyspace velocities may be in the range of about 0.1 h⁻¹ to about 10 h⁻¹.When operating hydroformylation unit 116 as a batch process, reactiontimes may vary from about 0.1 hours to about 10 hours or even longer.

Reaction temperatures in hydroformylation unit 116 may range from about100° C. to about 300° C. In certain embodiments, reaction temperaturesin the hydroformylation unit ranging from about 125° C. to about 250° C.may be used. Pressure in hydroformylation unit 116 may range from about1 atmosphere (101 kPa) to about 300 atmospheres (30398 kPa). In anembodiment, a pressure from about 20 (2027 kPa) to about 150 atmospheres(15199 kPa) may be used. An amount of catalyst relative to the amount ofolefin to be hydroformylated may vary. Typical molar ratios of catalystto olefin in the second hydrocarbon stream may range from about 1:1000to about 10:1. A ratio of between about 1:10 and about 5:1 may be usedin certain embodiments. In an embodiment, a second stream may be addedto hydroformylation unit 116 to control reaction conditions. The secondstream may include solvents that do not interfere substantially with thedesired reaction. Examples of such solvents include, but are not limitedto, alcohols, ethers, acetonitrile, sulfolane and paraffins.

Mono-alcohol selectivities of at least 90 percent and even of at least92 percent may be achieved in hydroformylation unit 116. In addition,olefin conversions to aliphatic alcohols may range from about 50 percentby weight to greater than 95 percent by weight. In certain embodiments,olefin conversion to aliphatic alcohols may be greater than 75 percentby weight. In some embodiments, olefin conversion to aliphatic alcoholsmay be greater than 99 percent by weight.

Isolation of aliphatic alcohols produced from the hydroformylationreaction product stream may be achieved by generally known methods. Inan embodiment, isolation of the aliphatic alcohols includes subjectingthe produced aliphatic alcohols to a first distillation, asaponification, a water washing treatment and a second distillation.

The hydroformylation reaction mixture stream may enter separator 126 viathird conduit 128. In separator 126, the hydroformylation reactionproduct stream may be subjected to a first distillation step (e.g.,flash distillation or a short path distillation). In an embodiment, ashort path distillation may be used to produce at least two streams, abottom stream and a top stream. At least a portion of the bottom streammay be recycled to hydroformylation unit 116 via bottom stream recycleconduit 130, in certain embodiments. The top stream may include, but isnot limited to, paraffins, unreacted olefins and a crude aliphaticalcohol product.

In an embodiment, a top stream may be subjected to a saponificationtreatment to remove any acids and esters present in the stream.Saponification may be performed by contacting the top stream with anaqueous solution of a hydroxide base (e.g., sodium hydroxide orpotassium hydroxide) at elevated temperatures with agitation. Thesaponification may be carried out by contacting the top stream with anaqueous 0.5 percent to 10 percent hydroxide base solution at a crudealcohol/water ratio of 10:1 to 1:1. The amount of hydroxide base usedmay depend on an estimated amount of esters and acids present.

Saponification of the top stream may be carried out batch-wise orcontinuously. The top stream may be subjected to one or moresaponification processes. Saponification reaction temperatures may befrom about 40° C. to about 99° C. In an embodiment, saponificationtemperatures may range from about 60° C. to about 95° C. Mixing of thetop stream with the basic water layer may be performed during thesaponification reaction. Separation of the top stream from the basicwater layer may be performed using known methods. The top stream may besubjected to a water wash after separation to remove any sodium saltspresent. The top stream may be separated using generally knowntechniques (e.g., fractional distillation) to produce at least twostreams, a crude alcohol product stream and a paraffins and unreactedolefins stream. As used herein, “fractional distillation” refers to thedistillation of liquids and subsequent collection of fractions ofliquids determined by boiling point. The paraffins and unreacted olefinsstream may be recycled, transported to other units for processing,stored on site, transported offsite and/or sold.

In certain embodiments, a crude aliphatic alcohol product stream maycontain unwanted by-products (e.g., aldehydes, hemi-acetals). Theby-products may be removed by subjecting the crude alcohol productstream to a hydrofinishing treatment step to produce an aliphaticalcohol product stream. “Hydrofinishing,” as used herein, refers to ahydrogenation reaction carried out under relatively mild conditions.Hydrofinishing may be carried out using conventional hydrogenationprocesses. Conventional hydrogenation processes may include passing thecrude alcohol feed together with a flow of hydrogen over a bed of asuitable hydrogenation catalyst. The aliphatic alcohol product streammay include greater than 50 percent by weight of the produced aliphaticalcohols. In some embodiments, the aliphatic alcohol product stream mayinclude greater than 80 percent by weight of the produced aliphaticalcohols. In other embodiments, the aliphatic alcohol product stream mayinclude greater than 95 percent by weight of the produced aliphaticalcohols. The aliphatic alcohol product stream may include branchedaliphatic primary alcohols. The resulting aliphatic alcohols in thealiphatic alcohol product stream may be sold commercially, transportedoff-site, stored on site and/or used in other processing units viaproduct conduit 132.

The composition of an aliphatic alcohol product stream may includehydrocarbons with an average carbon number ranging from 8 to 19. In anembodiment, an average carbon number of the hydrocarbons in aliphaticalcohol product stream may range from 10 to 17. In certain embodiments,an average carbon number of the feed stream may range from 10 to 13. Inother embodiments, an average carbon number of the feed stream may rangefrom 14 to 17. The aliphatic alcohol product stream may include branchedprimary alcohols. The branched primary alcohol product may be suitablefor the manufacture of anionic, nonionic and cationic surfactants. Insome embodiments, branched primary alcohol products may be used as theprecursor for the manufacture of anionic sulfates, including aliphaticsulfates and oxyalkyl sulfates and oxyalkyl alcohols.

Aliphatic alcohols may have slightly higher aliphatic branching andslightly higher number of quaternary carbons as the olefin precursor. Insome embodiments, aliphatic branching may include methyl and/or ethylbranches. In other embodiments, aliphatic branching may include methyl,ethyl and higher aliphatic branching. In certain embodiments, a numberof quaternary carbon atoms in the aliphatic alcohol product may be lessthan 0.5. In other embodiments, a number of quaternary carbon atoms inthe aliphatic alcohol product may be less than 0.3. Branching of thealcohol product may be determined by ¹H NMR analysis. The number ofquaternary carbon atoms may be determined by ¹³C NMR. A ¹³C NMR methodfor determining quaternary carbon atoms for branched aliphatic alcoholsis described in U.S. Pat. No. 6,150,322 to Singleton et al., entitled,“Highly Branched Primary Alcohol Compositions and BiodegradableDetergents Made Therefrom,” which is incorporated by reference herein.

In certain embodiments, at least a portion of the paraffins andunreacted olefins stream may be combined with the first hydrocarbonstream in first conduit 112 to produce a combined stream via fourthconduit 134. The combined stream may be introduced intodehydrogenation-isomerization unit 110 via first conduit 112. At least aportion of the olefins in the combined stream may be isomerized tobranched olefins. In some embodiments, at least a portion of theparaffins and unreacted olefins stream is introduced directly intodehydrogenation-isomerization unit 110 via one or more entry points.Because the paraffins and unreacted olefins stream containing paraffinsand unreacted olefins may be recycled to dehydrogenation-isomerizationunit 110 as one stream, the process may be more efficient, resulting inan overall higher throughput. The higher throughput will increase theoverall yield of the aliphatic alcohols.

In some embodiments, an olefins and paraffins concentration inhydroformylation unit 116 may be adjusted depending on the source of theolefin stream entering the hydroformylation unit. A third hydrocarbonstream may be added upstream of hydroformylation unit 116 to produce acombined stream. In other embodiments, a third hydrocarbon stream may beintroduced directly into hydroformylation unit 116 through one or morepoints. A third hydrocarbon stream may be introduced into second conduit114 via fifth conduit 136 to produce a combined stream as depicted inFIG. 4. The combined stream may enter hydroformylation unit 116 viasecond conduit 114 to continue the process to produce aliphaticalcohols.

The third hydrocarbon stream may be from the same source as the firsthydrocarbon stream. In some embodiments, a third hydrocarbon stream maybe a hydrocarbon stream that includes olefins, paraffins, and/orhydrocarbon solvents derived from another source. The third hydrocarbonstream may include olefins and paraffins. In certain embodiments, anaverage carbon number of the hydrocarbons in the third hydrocarbonstream ranges from 7 to 18. In some embodiments, a paraffin content ofthe third hydrocarbon stream may be between about 60 percent and about90 percent by weight. In other embodiments, a paraffin content of thethird hydrocarbon stream may be greater than 90 percent by weight.

In an embodiment, an olefin content of a third hydrocarbon stream rangesbetween about 1 percent and about 99 percent relative to the totalhydrocarbon content. In certain embodiments, an olefin content of thethird hydrocarbon stream may be between about 45 percent and about 99percent by weight. In other embodiments, an olefin concentration of thethird hydrocarbon stream may be greater than 80 percent by weight.

In certain embodiments, dehydrogenation-isomerization unit 110 may beseparated into a plurality of zones to control reaction temperaturesand/or prevent unwanted side reactions (e.g., diene formation and/orcyclization reactions). A first hydrocarbon stream containing paraffinsand unreacted olefins may be introduced intodehydrogenation-isomerization unit 110 via first conduit 112 as depictedfor System 200 in FIG. 5. In some embodiments, a first hydrocarbonstream includes alpha-olefins. Hydrocarbons in the first hydrocarbonstream may have an average carbon number from 7 to 18. In otherembodiments, hydrocarbons in the first hydrocarbon stream may have anaverage carbon number from 10 to 17. In some embodiments, hydrocarbonsin the first hydrocarbon stream may have an average carbon number from14 to 17. In certain embodiments, hydrocarbons in the first hydrocarbonstream may have an average carbon number from 10 to 13. An alpha-olefincontent of the first hydrocarbon stream may be greater than 70 percentof the total amount of olefins in the first hydrocarbon stream. Incertain embodiments, a first hydrocarbon stream is produced from aFischer-Tropsch process. Dehydrogenation-isomerization unit 110 may bedivided into a plurality of zones. The plurality of zones may include,but is not limited to, a first reaction zone, a transition zone and asecond reaction zone. In first reaction zone 210, at least a portion ofthe paraffins in the first hydrocarbon stream may be dehydrogenated toolefins to produce an olefinic stream. The process stream may then passinto second reaction zone 212. In second reaction zone 212, at least aportion of the olefins in the process stream may be isomerized tobranched olefins to produce a second hydrocarbon stream.

In first reaction zone 210, the dehydrogenation catalyst may be selectedfrom a wide range of catalyst types. For example, the catalyst may bebased on a metal or metal compound deposited on a porous support. Themetal or metal compound may be selected from, but is not limited to,chrome oxide, iron oxide and noble metals.

Techniques of preparing catalysts, for performing the dehydrogenationstep and for performing associated separation steps are known in theart. For example, suitable procedures for preparing catalysts andperforming the dehydrogenation step are described in U.S. Pat. No.5,012,021 to Vora et al., entitled “Process For the Production of AlkylAromatic Hydrocarbons Using Solid Catalysts;” U.S. Pat. No. 3,274,287 toMoore et al., entitled “Hydrocarbon Conversion Process and Catalyst;”U.S. Pat. No. 3,315,007 to Abell et al., entitled “Dehydrogenation ofSaturated Hydrocarbons Over Noble-Metal Catalyst;” U.S. Pat. No.3,315,008 to Abell et al., entitled “Dehydrogenation of SaturatedHydrocarbons Over Noble-Metal Catalyst;” U.S. Pat. No. 3,745,112 toRausch, entitled “Platinum-Tin Uniformly Dispersed HydrocarbonConversion Catalyst and Process;” U.S. Pat. No. 4,506,032 to Imai etal., entitled “Dehydrogenation Catalyst Composition” and U.S. Pat. No.4,430,517 to Imai et al., entitled “Dehydrogenation Process Using aCatalytic Composition,” all of which are incorporated by referenceherein.

Reaction temperatures in first reaction zone 210 may range from about300° C. to about 600° C. In some embodiments, a reaction temperature infirst reaction zone 210 may range from about 450° C. to about 550° C. Atotal pressure in first reaction zone 210 may range from about 0.010atmosphere (1 kPa) to about 25.0 atmospheres (2534 kPa). In certainembodiments, total pressure in first reaction zone 210 may range fromabout 0.010 atmospheres (1 kPa) to about 15.0 atmospheres (1520 kPa). Insome embodiments, hydrogen may be fed together with the unreacted firsthydrocarbon stream in order to prevent coking. Hydrogen and paraffinspresent in the unreacted first hydrocarbon stream may be fed at ahydrogen to paraffin molar ratio in a range from about 0.1 to about 20.In an embodiment, a hydrogen to paraffin molar ratio may be in a rangeof about 1 to about 10.

Residence time in first reaction zone 210 may be selected such that aconversion level of the paraffins to olefins is below about 50 molepercent. In certain embodiments, a conversion level of the paraffins toolefins may be kept in a range from about 10 mole percent to about 20mole percent. By keeping the conversion level low, side reactions (e.g.,diene formation and cyclization reactions) may be prevented. In someembodiments, an olefinic hydrocarbon stream may exit first reaction zone210, pass through transition zone 214 and enter second reaction zone212. Transition zone 214 may include heat exchanger 216. Heat exchanger216 may reduce the temperature of the olefinic hydrocarbon stream. In anembodiment, first reaction zone 210 and second reaction zone 212 indehydrogenation-isomerization unit 110 may be separate units, asdepicted in FIG. 5B, with heat exchanger 216 positioned between the twounits.

After the olefinic hydrocarbon stream enters second reaction zone 212,at least a portion of the olefins are isomerized to branched olefins toproduce a second hydrocarbon stream. The composition and level ofbranching of the second hydrocarbon stream may be performed by ¹H NMRanalysis. In an embodiment, an olefinic stream may exit first reactionzone 210 and directly enter second reaction zone 212 where at least aportion of the olefins in the olefinic stream are isomerized to branchedolefins.

The catalyst used for isomerization of the olefins to branched olefinsmay be the same as described in U.S. Pat. No. 5,648,584 to Murray,entitled “Process for Isomerizing Linear Olefins to Isoolefins” and U.S.Pat. No. 5,648,585 to Murray et al., entitled “Process for IsomerizingLinear Olefins to Isoolefins” both of which are incorporated herein byreference.

In an embodiment, linear olefins in a first hydrocarbon stream areisomerized in second reaction zone 212 by contacting at least a portionof the olefinic stream with a zeolite catalyst. The zeolite catalyst mayhave at least one channel with a crystallographic free channel diameterranging from greater than 4.2 Å to less than 7 Å. The zeolite catalystmay have an elliptical pore size large enough to permit entry of alinear olefin and at least partial diffusion of a branched olefin. Thepore size of the zeolite catalyst may also be small enough to retardcoke formation.

Temperatures in second reaction zone 212 may be from about 200° C. toabout 500° C. to isomerize linear olefins to branched olefins. In someembodiments, reaction temperatures in the first reaction zone and thesecond reaction zone are substantially the same. In such embodiments,use of a heat exchanger is not required. Typically, however, thereaction temperature of second reaction zone 212 is less than thereaction temperature of the first reaction zone. The use of a heatexchanger lowers the temperature of the stream leaving the firstreaction zone to the appropriate temperature for reaction in the secondreaction zone. Hydrocarbon partial pressure in the second reaction zonemay be from about 0.1 atmosphere (10 kPa) to about 10 atmospheres (1013kPa).

In some embodiments, the second hydrocarbon stream may exit a secondreaction zone and enter a separation unit. In the separation unit,branched olefins may be separated from linear olefins and paraffins aspreviously described with regard to FIG. 3. Referring to FIG. 5, thesecond hydrocarbon stream may exit second reaction zone 212 via secondconduit 114 and enter hydroformylation unit 116. At least a portion ofthe olefins in the second hydrocarbon stream may be hydroformylated toproduce a hydroformylation reaction stream as described for System 100.At least a portion of the hydroformylation reaction stream may beseparated into a bottom stream and a top stream using generally knownmethods. The crude aliphatic alcohol product stream may be furtherpurified as described for System 100 to produce a paraffins andunreacted olefins stream and an aliphatic alcohol product stream. Thealiphatic alcohol product stream may include branched aliphatic alcohols(e.g., branched primary aliphatic alcohols). The aliphatic alcoholproduct stream may be recycled, transported to other processing units,sold, and/or transported to storage vessels.

The hydroformylation reaction mixture stream may enter separator 126 viathird conduit 128. In separator 126, at least three streams, a bottomstream, a paraffins and unreacted olefins stream and an aliphaticalcohol product stream, may be produced using techniques previouslydescribed for System 100. At least a portion of the bottom stream may berecycled to the hydroformylation unit via bottom stream recycle conduit130. At least a portion of the paraffins and unreacted olefins streammay be recycled combined with other process streams, transported toand/or stored on site. The aliphatic alcohol product stream may betransported via product conduit 132 to be stored on site, soldcommercially, transported off-site and/or utilized in other processingunits.

In an embodiment, at least a portion of the paraffins and unreactedolefins stream may be combined with the first hydrocarbon stream toproduce a combined hydrocarbon stream via fourth conduit 134. Thecombined hydrocarbon stream may enter first reaction zone 210 andundergo the dehydrogenation-isomerization process and hydroformylationprocess to produce aliphatic alcohols. By recycling the paraffins andunreacted olefins stream, the yield of product may be maximized. In anembodiment, a paraffins and unreacted olefins stream may directly enterdehydrogenation-isomerization unit 110 through one or more points ofentry.

In some embodiments, an olefins and paraffins concentration inhydroformylation unit 116 may be adjusted depending on the source of theolefin stream entering the hydroformylation unit as previously describedfor System 100. At least a portion of a third hydrocarbon stream may beintroduced into second conduit 114 upstream of hydroformylation unit 116via fifth conduit 136. The combined stream may be introduced intohydroformylation unit 116 via second conduit 114. At least a portion ofthe olefins in the combined stream may be hydroformylated to producealiphatic alcohols. In an embodiment, a third hydrocarbon stream may beintroduced directly into hydroformylation unit 116 through one or morepoints of entry.

A third hydrocarbon stream may be used to optimize the olefinconcentration in hydroformylation unit 116 at a concentration sufficientto maximize hydroformylation of the olefin. In addition, the thirdhydrocarbon may optimize the ratio of linear to branched aliphaticgroups in the aliphatic alcohol. The third hydrocarbon stream may be,but is not limited to, a hydrocarbon stream containing olefins,paraffins and/or hydrocarbon solvents.

In an embodiment, a third hydrocarbon stream includes a paraffin contentof between about 50 percent and about 99 percent relative to the totalhydrocarbon content. In certain embodiments, a paraffin content of thethird hydrocarbon stream ranges between 60 percent and 90 percentrelative to the total hydrocarbon content. In other embodiments, aparaffin content of the third hydrocarbon stream is greater than 80percent relative to the total hydrocarbon content.

In an embodiment, an olefin content of a third hydrocarbon stream rangesbetween about 1 percent and about 99 percent relative to the totalhydrocarbon content. In other embodiments, an olefin content of a thirdhydrocarbon stream may be greater than 80 percent relative to the totalhydrocarbon stream.

In an embodiment, a catalyst in dehydrogenation-isomerization unit 110may be used in a stacked bed configuration. A stacked bed configurationmay allow for the use of one or more catalysts in the reactor. Acatalyst for dehydrogenation of paraffins and a catalyst forisomerization of olefins may enhance the selectivity of the catalystsand/or the process. A stacked bed configuration ofdehydrogenation-isomerization unit 110 is depicted for System 300 inFIG. 6. Operating conditions of the stacked bed configuration may be thesame as for two-zone system described above for System 200. The firsthydrocarbon stream may enter the dehydrogenation zone 310 via firstconduit 112.

The dehydrogenation catalyst used in the stacked bed configuration mayhave nonacidic properties. The term “nonacidic,” as used herein, refersto a catalyst that exhibits little skeletal isomerization activity. Thedehydrogenation catalyst may include a noble metal, a Group IVAcomponent, an alkali or alkaline earth component, a halogen componentand/or a porous carrier material.

In certain embodiments, a noble metal may be dispersed throughout thedehydrogenation catalyst. An amount of noble metal may range betweenabout 0.01 weight percent to about 5 weight percent, calculated on anelemental basis, of the final dehydrogenation catalyst. In certainembodiments, a dehydrogenation catalyst includes about 0.1 weightpercent to about 1 weight percent platinum. The noble metal may beincorporated into the catalytic composite by techniques known in the art(e.g., co-precipitation, co-gelation, ion exchange, impregnation,deposition from a vapor phase or from an atomic source) beforeincorporation of other catalytic components. In some embodiments, anoble metal may be incorporated into the catalytic composite duringincorporation of other catalytic components. In other embodiments, anoble metal may be incorporated into the catalytic composite afterincorporation of other catalytic components. In certain embodiments, anoble metal may be incorporated by impregnation of the carrier materialwith a solution or suspension of a decomposable compound of the noblemetal. For example, platinum may be added to a catalytic support bycommingling the platinum with an aqueous solution of chloroplatinicacid. In other embodiments, optional components (e.g., nitric acid) maybe added to the impregnating solution to assist in dispersing or fixingthe noble metal in the final catalyst composite.

The Group IVA component, may include germanium, tin, lead orcombinations thereof. In some embodiments, a Group IVA component mayexist within the catalyst in an oxidation state above that of the noblemetal. The Group IVA component may be present as an oxide. In certainembodiments, a Group IVA component may be combined with a carriermaterial. In some embodiments, a Group IVA component may be combinedwith the other catalytic components. In other embodiments, a Group IVAcomponent may be dispersed throughout the catalyst. A Group IVAcomponent may range between about 0.01 weight percent to about 5 weightpercent, calculated on an elemental basis, of the final catalystcomposite. In some embodiments, a catalyst includes about 0.2 weightpercent to about 2 weight percent tin.

The Group IVA component may be incorporated in the catalytic compositeaccording to generally known methods (e.g., co-precipitation,co-gelation, ion exchange and impregnation) before other catalyticcomponents are incorporated. In some embodiments, a Group IVA componentmay be incorporated during incorporation of other catalytic components.In other embodiments, a Group IVA component may be incorporated afterother catalytic components are incorporated. In some embodiments, a tincomponent may be incorporated by co-gelation with the porous carriermaterial. The tin may be incorporated in an alumina carrier material bymixing a soluble tin compound (e.g., stannous or stannic chloride) withan alumina hydrosol. A gelling agent (e.g., hexamethylenetetraamine) maybe added to the tin-alumina hydrosol mixture. The tin-alumina hydrosolmixture may be dropped into an oil bath to form spheres containingalumina and tin. In other embodiments, a germanium component may beimpregnated into a carrier material with a solution or suspension of adecomposable compound of germanium (e.g., germanium tetrachloridedissolved in an alcohol). In other embodiments, a lead component may beimpregnated from a solution of lead nitrate in water.

In certain embodiments, an alkali or alkaline earth component may beincluded in the dehydrogenation catalyst. Alkali and alkaline earthcomponent may include, but is not limited to, cesium, rubidium,potassium, sodium, lithium, barium, strontium, calcium and magnesium ormixtures thereof. The alkali or alkaline earth component may exist inthe final catalytic composite in an oxidation state above that of thenoble metal. The alkali or alkaline earth component may be present as anoxide. In some embodiments, an alkali or alkaline earth metal may becombined with the carrier material. In certain embodiments, an alkali oralkaline earth metal may be combined with other dehydrogenationcatalytic components.

In other embodiments, an alkali or alkaline earth component may bedispersed throughout the catalytic composite. An amount of alkali oralkaline earth component may range from about 0.01 weight percent to 15weight percent, calculated on an elemental basis, of the final catalyticcomposite. In other embodiments, a dehydrogenation catalyst includesabout 1 weight percent to about 3 weight percent potassium. In certainembodiments, an atomic ratio of the alkali or alkaline earth componentto the noble metal may be greater than at least about 10.

The alkali or alkaline earth component may be incorporated in thecatalytic composite according to generally known methods (e.g.,co-precipitation, co-gelation, ion exchange or impregnation) beforeother catalytic components are incorporated. In some embodiments, analkali or alkaline earth component may be incorporated duringincorporation of other catalytic components. In other embodiments, analkali or alkaline earth component may be incorporated after othercatalytic components are incorporated. For example, a potassiumcomponent may be impregnated into the carrier material with a solutionof potassium nitrate. An atomic ratio of alkali or alkaline earthcomponent to noble metal may be at least about 10. In certainembodiments, an atomic ratio of the alkali or alkaline earth componentto the noble metal component may range from about 15 to about 25.

A porous carrier material used in a dehydrogenation catalyst may includea porous, absorptive support with high surface area from about 25 m²/gto about 500 m²/g. The porous carrier material may have a melting pointgreater than the conditions utilized in the dehydrogenation zone.Examples of carrier materials include, but are not limited to, activatedcarbon, coke, charcoal, silica, silica gel, silicon carbide,synthetically prepared and/or naturally occurring clays and silicates,refractory inorganic oxides, crystalline zeolitic aluminosilicates,naturally occurring or synthetically prepared mordenite and/orfaujasite, spinels or combinations of thereof. In certain embodiments, acarrier material may be gamma- or eta-alumina. In some embodiments,clays and silicates may or may not be acid treated (e.g., attapulgite,china clay, diatomaceous earth, fuller's earth, kaolin, kieselguhr,ceramics, porcelain, crushed firebrick, bauxite). Examples of refractoryinorganic oxides include alumina, titanium dioxide, zirconium dioxide,chromium oxide, beryllium oxide, vanadium oxide, cerium oxide, hafniumoxide, zinc oxide, magnesia, boria, thoria, silica-alumina,silica-magnesia, chromia-alumina, alumina-boria, and silica-zirconia.Zeolitic aluminosilcates may be, in some embodiments, in the hydrogenform. In other embodiments, zeolitic aluminosilcates may be in a formthat may be exchanged with metal cations. Examples of spinels include,but are not limited to, MgAl₂O₄, FeAl₂O₄, ZnAl₂O₄, CaAl₂O₄, and otherlike compounds having the formula MO—Al₂O₃ in which M is a metal havinga valence of 2.

In certain embodiments, an alumina carrier material used in adehydrogenation catalyst may be prepared in any suitable manner fromsynthetic or naturally occurring raw materials. The alumina carrier maybe formed in any desired shape (e.g., spheres, pills, cakes, extrudates,powders, granules). The alumina carrier may be utilized in any particlesize. In certain embodiments, a sphere shape may be utilized. Theparticle may be about 1/16 inch in diameter. In certain embodiments, aparticle diameter of less than 1/32 inch may be utilized.

Alumina spheres may be prepared, in some embodiments, by convertingaluminum metal into an alumina sol. An alumina sol may be prepared byreacting aluminum metal with a suitable peptizing acid and water. Theresulting alumina sol and a gelling agent may be dropped into an oilbath to form spherical particles of an alumina gel. The resultingalumina gel may be converted to gamma- or eta-alumina carrier materialusing known techniques (e.g., by aging, drying and calcining).

In other embodiments, alumina cylinders may be prepared by mullingalumina powder with water and a suitable peptizing agent (e.g., nitricacid) to form an extrudable composition. The composition may be extrudedthrough a suitably sized die then cut to form extrudate particles. Othershapes of the alumina carrier material may be prepared by conventionalmethods. After the alumina particles are shaped, they may be dried andcalcined. The alumina carrier may be subjected to intermediatetreatments (e.g., washing with water or a solution of ammoniumhydroxide) during preparation.

The dehydrogenation catalyst may include a halogen component. Thehalogen component may include, but is not limited to, fluorine,chlorine, bromine, iodine or mixtures thereof. The halogen component maybe present in a combined state with the porous carrier material. Incertain embodiments, a halogen component may be dispersed throughout thecatalytic composite. A halogen component may range from at least about0.2 weight percent to about 15 weight percent, calculated on anelemental basis, of the final catalytic composite. In certainembodiments, a dehydrogenation catalyst contains about 1 weight percentto about 3 weight percent chlorine.

In certain embodiments, a catalyst composition may include at leastabout 0.2 weight percent, calculated on an elemental basis, of a halogencomponent. The halogen component in the catalyst may improve theactivity of the catalyst for dehydrogenating hydrocarbons. In someembodiments, an active halogen component may suppress carbon formationon the catalyst during the dehydrogenation process. An advantage of thecatalyst composition may be that undesirable isomerization or crackingside reactions may be inhibited. In certain embodiments, halogen contentmay increase the acidity of the catalyst. The acidity may be lowered bysteaming the dehydrogenation catalyst to remove excess halogen from thedehydrogenation catalyst.

A halogen component may be incorporated in the catalytic composite inany suitable manner. The incorporation of the halogen may be beforepreparation of the carrier material. In some embodiments, incorporationof a halogen may be during incorporation of other catalytic components.In other embodiments, incorporation of a halogen may be after othercatalytic components are incorporated. In certain embodiments, analumina sol carrier may contain a halogen, which may contribute to atleast some portion of the halogen content in the final catalystcomposite. In some embodiments, a halogen component, or a portionthereof, may be added to the catalyst composite during the incorporationof the carrier material with other catalyst components (e.g., usingchloroplatinic acid to impregnate the platinum component). In otherembodiments, a halogen component or a portion thereof may be added tothe catalyst composite by contacting the catalyst with the halogen. Insome embodiments, a halogen may be added to the catalyst as a compound,solution, suspension or dispersion containing the halogen, (e.g.,hydrochloric acid) before or after other catalyst components areincorporated with the carrier material. In certain embodiments, ahalogen component or a portion thereof may be incorporated by contactingthe catalyst with a compound, solution, suspension or dispersioncontaining the halogen in a subsequent catalyst regeneration step. Inthe regeneration step, carbon deposited on the catalyst as coke duringuse of the catalyst in a hydrocarbon conversion process may be burnedoff the catalyst. The noble metal on the catalyst may be redistributedto provide a regenerated catalyst with performance characteristicssimilar to those of the fresh catalyst. The halogen component may beadded during the carbon burn step or during the noble metalredistribution step (e.g., contacting the catalyst with a hydrogenchloride gas). In some embodiments, a halogen component may be added tothe catalyst composite by adding the halogen or a compound, solution,suspension or dispersion containing the halogen (e.g., propylenedichloride) to the hydrocarbon feed stream. In other embodiments, ahalogen component may be added to the recycle gas during operation ofthe dehydrogenation unit.

In some embodiments, a dehydrogenation catalyst may include a sulfurcomponent ranging from about 0.01 weight percent to about 10 weightpercent, calculated on an elemental basis, of the final catalyticcomposition. The sulfur component may be incorporated into the catalyticcomposite in any suitable manner. In certain embodiments, sulfur or acompound containing sulfur (e.g., hydrogen sulfide or a lower molecularweight mercaptan) may be contacted with the catalyst composition in thepresence of hydrogen at a temperature ranging from about 10° C. to about540° C. under anhydrous conditions. A hydrogen to sulfur ratio, in someembodiments, may be about 100.

The dehydrogenation catalyst, in some embodiments, may also containother, additional components or mixtures thereof, which act alone or inconcert, as catalyst modifiers to improve catalyst activity, selectivityor stability. Examples of catalyst modifiers include, but are notlimited to, antimony, arsenic, beryllium, bismuth, cadmium, calcium,chromium, cobalt, copper, gallium, gold, indium, iron, lithium,manganese, molybdenum, nickel, rhenium, scandium, silver, tantalum,thallium, titanium, tungsten, uranium, zinc and zirconium. Catalyticmodifiers may be added in any suitable manner to the carrier materialduring preparation of the dehydrogenation catalyst. In otherembodiments, catalytic modifiers may be added in any suitable mannerafter preparation of the dehydrogenation catalyst. In some embodiments,catalytic modifiers may be added in any suitable manner to the catalyticcomposite before other catalytic components are incorporated. In certainembodiments, catalytic modifiers may be added during incorporation ofother catalytic components. In other embodiments, catalytic modifiersmay be added after other catalytic components are incorporated. Adescription of a dehydrogenation catalyst may be found in U.S. Pat. No.4,506,032 to Imai et al., entitled “Dehydrogenation CatalystComposition,” which is incorporated by reference herein.

The olefinic hydrocarbon stream may pass into isomerization zone 312. Incertain embodiments, a temperature decrease from dehydrogenation zone310 to isomerization zone 312 may be necessary to prevent cracking ofthe olefinic hydrocarbon stream as it enters the isomerization zone.Cool hydrogen gas may be introduced to dehydrogenation zone 310 via gasconduit 314 to control temperatures in dehydrogenation zone 310. Inisomerization zone 312, at least a portion of the olefins in theolefinic hydrocarbon stream may be isomerized to branched olefins toproduce a second hydrocarbon stream.

In certain embodiments, an isomerization catalyst may be the same asdescribed for isomerization of olefins in System 200. A description ofthe isomerization catalyst may be found in U.S. Pat. No. 5,510,306 toMurray, entitled “Process For Isomerizing Linear Olefins to Isoolefins,”which is incorporated by reference herein. In some embodiments, about0.01 weight percent to about 5 weight percent of a noble metal may beadded to an isomerization catalyst used in a stacked bed configurationto increase the dehydrogenation activity of the zeolitic catalyst.Common metal incorporation methods (e.g., impregnation, noble metal ionexchange, co-mulling) may be used to incorporate a noble metal (e.g.,platinum, palladium) into a zeolite to produce a working catalyst usefulin the dehydrogenation-isomerization of paraffins.

The second hydrocarbon stream may exit isomerization zone 312 and enterhydroformylation unit 116 via second conduit 114. At least a portion ofthe olefins in the second hydrocarbon stream may be hydroformylated toproduce a hydroformylation reaction stream as described for System 100.At least a portion of the hydroformylation reaction stream may beseparated into a bottoms stream and a top stream using generally knownmethods. The top stream may be purified and separated as described forSystem 100 to produce a paraffins and unreacted olefins stream and acrude aliphatic alcohol product stream. The crude aliphatic alcoholproduct stream may be further purified as described for System 100 toproduce an aliphatic alcohol product stream. The hydroformylationreaction mixture stream may enter separator 126 via third conduit 128.In separator 126 at least two streams, a bottom stream and top stream,may be produced as previously described for System 100. The bottomstream may be recycled to hydroformylation unit 116 via bottom streamrecycle conduit 130. The top stream may be purified and separated intoat least two streams, a paraffins and unreacted olefins stream and acrude aliphatic alcohol product stream. At least a portion of theparaffins and unreacted olefins stream may be recycled, combined withother process streams, sent to other processing units and/or sent to astorage vessel. The crude aliphatic alcohol product stream may befurther purified as described for System 100 to produce an aliphaticalcohol product stream. The aliphatic alcohol product stream may includebranched aliphatic alcohols (e.g., branched primary aliphatic alcohols).The aliphatic alcohol product stream may be transported via productconduit 132 to be stored on site, sold commercially, transportedoff-site and/or utilized in other processing units.

At least a portion of the paraffins and unreacted olefins stream may becombined with the first hydrocarbon stream in first conduit 112 toproduce a combined hydrocarbon stream via fourth conduit 134. Thecombined hydrocarbon stream may enter dehydrogenation zone 310 ofdehydrogenation-isomerization unit 110 via first conduit 112. Thecombined hydrocarbon stream entering dehydrogenation zone 310 continuesthe dehydrogenation-isomerization process and hydroformylation processto produce aliphatic alcohols. By recycling the paraffins and unreactedolefins stream, the yield of product may be maximized. In an embodiment,a paraffins and unreacted olefins stream may directly enterdehydrogenation-isomerization unit 110 through one or more entry points.

In some embodiments, an olefin and paraffin concentration inhydroformylation unit 116 may be adjusted depending on the source of theolefin stream entering the hydroformylation unit. At least a portion ofa third hydrocarbon stream may be introduced into the second conduitupstream of the hydroformylation unit as previously described for System100. The combined stream may be introduced into hydroformylation unit116 via second conduit 114. At least a portion of the olefins in thecombined stream may be hydroformylated to produce aliphatic alcohols.

In an embodiment, a third hydrocarbon stream includes a paraffin contentbetween about 50 percent and about 99 percent relative to the totalhydrocarbon content. In certain embodiments, a paraffin content of thethird hydrocarbon stream ranges between 60 percent and 90 percentrelative to the total hydrocarbon content. In other embodiments, aparaffin content of the third hydrocarbon stream may be greater than 80percent relative to the total hydrocarbon content.

In an embodiment, an olefin content of a third hydrocarbon stream rangesbetween about 1 percent and about 99 percent relative to the totalhydrocarbon content. In other embodiments, an olefin content of a thirdhydrocarbon stream may be greater than 80 percent relative to the totalhydrocarbon stream.

In certain embodiments, a Fischer-Tropsch feed stream may containolefins and paraffins of low carbon number (e.g., 4, 5, 6, 7, 8, 9).Typically, a low carbon number feed stream may be sold as fuel, sent towaste and/or recycled to other processing units. The low carbon numberfeed stream may be less useful in the production of detergents.Typically detergents are made from olefins having a carbon numbergreater than 7. Conversion of the olefins in the feed stream to branchedolefins with higher average carbon number (e.g., 7 to 18) may result ina more commercially valuable use of a low carbon number feed stream(e.g., processed to produce detergents and/or surfactants). The amountand type of branching of the alkyl group may increase the value of thefeed stream.

A first hydrocarbon stream, including olefins and paraffins may betransported to dimerization unit 410 via first conduit 412 as depictedfor System 400 in FIG. 7. Hydrocarbons in the first hydrocarbon streammay have an average carbon number from 4 to 9. In certain embodiments,hydrocarbons in a first hydrocarbon stream may have an average carbonnumber from 5 to 8. In some embodiments, hydrocarbons in a firsthydrocarbon stream may have an average carbon number from 5 to 7. Inother embodiments, hydrocarbons in a first hydrocarbon stream may havean average carbon number from 5 to 9. A first hydrocarbon stream may, insome embodiments, be derived from a Fischer-Tropsch process. Indimerization unit 410, at least a portion of the olefins may bedimerized. At least a portion of the dimerized olefins exit dimerizationunit 410 as a second hydrocarbon stream via second conduit 414.Depending on the choice of catalyst, the resulting dimer may bebranched. The branches of the olefin produced in dimerization unit 410may include methyl, ethyl and/or longer carbon chains. In an embodiment,dimerized olefins may contain greater than 50 percent methyl branches.In certain embodiments, dimerized olefins may contain greater than 90percent methyl branches. The dimerized olefins may be separated from theunreacted products through techniques known in the art. One suchtechnique is fractional distillation. At least a portion of theparaffins and unreacted olefins may be separated and recycled back tothe dimerization unit and/or sent to other processing units.

In certain embodiments, dimerization unit 410 may have several points ofentry to accommodate process streams that vary in composition. Processstreams may be from other processing units and/or storage units.Examples of process streams include a diluent hydrocarbon stream, and/orother hydrocarbon streams that include olefins and paraffins derivedfrom other processes. Examples of other processes may include ShellHigher Olefins Process or wax cracking process. As used herein, “entryinto the dimerization unit” refers to entry of process streams into thedimerization unit through one or more entry points.

A dimerization catalyst used in dimerization unit 410 may be ahomogeneous or heterogeneous catalyst. In certain embodiments, adimerization catalyst used in dimerization unit 410 may be a catalystthat includes oxides of Group III, Group IVA, Group IVB, Group VIIIA, orcombinations thereof. Examples of such oxides include, but are notlimited to, nickel oxide, silicon dioxide, titanium dioxide, aluminumoxide or zirconium dioxide. The dimerization catalyst may include anamorphous nickel oxide (NiO) present as a dispersed substantialmonolayer on the surfaces of a silica (SiO₂) support. The silica supportmay also include on the surface minor amounts of an oxide of aluminum,gallium or indium such that the ratio of nickel oxide to metal oxidepresent in the catalyst is within the range from about 4:1 to about100:1. The dimerization catalyst may be prepared by precipitating awater insoluble nickel salt onto the surface of a silica support. Thesilica support may be impregnated with a metal oxide. In otherembodiments, a dimerization catalyst may be prepared by precipitating awater insoluble nickel salt onto a silica-alumina support. Thesilica-alumina support may be dealuminized such that the resultingnickel oxide/alumina ratio falls within the range from about 4:1 toabout 100:1. The catalyst may be activated by calcination in thepresence of oxygen at a temperature with a temperature range from about300° C. to about 700° C. In some embodiments, the catalyst may beactivated by calcination in the presence of oxygen at a temperature witha temperature range from about 500° C. to about 600° C.

Silica useful as a support material may have a surface area within arange from about 100 m²/g to about 450 m²/g. In an embodiment, a silicasurface area may be within the range from about 200 m²/g to about 400m²/g. A range of nickel oxide content may be from about 7 percent toabout 70 percent by weight. In certain embodiments, a nickel oxidecontent may be from about 20 percent to about 50 percent by weight,depending on the surface area of the particular support utilized inpreparing the catalyst. For a silica support having a surface area ofabout 300 m²/g, a nickel oxide content may, in some embodiments, rangefrom about 21 percent to about 35 percent by weight. A nickel oxidecontent may, in other embodiments, be about 28 percent by weight.

The silica support may be in dry granular form or in a hydrogel formprior to precipitation of the nickel oxide precursor compound on thesurfaces thereof. Silica hydrogel may be prepared by mixing awater-soluble silicate, (e.g., a sodium or potassium silicate) with amineral acid. The water-soluble silicate may be washed with water toremove water-soluble ions. The resulting silica hydrogel may bepartially dried. In some embodiments, a silica hydrogel may becompletely dried.

A nickel oxide precursor may include a water-insoluble nickel salt, suchas nickel carbonate, nickel phosphate, nickel nitrate or nickelhydroxide. A water-insoluble nickel salt may be generated in-situ byforming an aqueous mixture of the silica gel and a water-soluble nickelsalt. The nickel salt may include, but is not limited to, nickelnitrate, nickel sulfonate, nickel carbonylate, nickel halide. A base maybe added to the aqueous mixture to induce precipitation of thewater-insoluble nickel salt. The water-insoluble nickel salt may beprecipitated in finely divided form within the interstices and on thesurface of the silica support. The treated silica support may then berecovered, washed several times and dried.

A second component in the catalyst may be a trivalent metal oxide, whichmay include, but is not limited to, aluminum, gallium and indium orcombinations thereof. Although a nickel oxide and/or silica catalyst maybe active for olefin dimerization, it may deactivate quickly.Deactivation may be from formation of large oligomers that remainattached to the catalyst surface. Large oligomers may act as cokeprecursors, in some embodiments. A presence of a small amount of thetrivalent metal oxide within the catalyst may form acid sites. Acidicsites may promote catalytic activity without promoting unwanted and/orexcessive oligomer formation.

A trivalent metal oxide may be incorporated into the silica support bygenerally known techniques (e.g., precipitation, impregnation). In anembodiment, a trivalent metal oxide may be impregnated into the silicasupport as an aqueous solution by the addition of a water-soluble salt.The water-soluble metal salt may include, but is not limited to, metalnitrates, metal chlorides or metal sulfates. Once impregnated with ametal salt, the silica support may be dried and calcinated to reduce themetal salt to the oxide form. The silica-trivalent oxide support mayfurther treated to incorporate a nickel oxide layer onto thesilica-trivalent metal oxide support.

In an embodiment, silica-trivalent metal oxide (e.g., silica/alumina,silica/gallia or silica/india gel) may be utilized as support material.In certain embodiments, a content of metal oxide (e.g., alumina) presentin the support may be low in comparison with the content of nickeloxide. Dealuminization of the silica/alumina gel of relatively highalumina content (e.g., above about 5 percent by weight) may be necessaryto reduce the content of alumina. Dealuminization may be accomplished byknown techniques (e.g., extraction of the aluminum with an organic orinorganic acid). Organic or inorganic acids may include, but are notlimited to, nitric acid, sulfuric acid, hydrochloric acid, chloroaceticacid or ethylene diamine tetraacetic acid. Extraction may beaccomplished by adding the acid to an aqueous dispersion of the aluminosilicate followed by stirring, decantation and washing with water. Theprocess may be repeated one or more times until the desired aluminacontent is achieved. The solids are then dried, calcined and furthertreated to incorporate the nickel oxide layer onto the silica/aluminasupport.

A content of trivalent metal oxide with respect to the content of thenickel oxide present in the silica support may be significant. Incertain embodiments, when the content of trivalent metal oxide is toolow (e.g., above a nickel oxide to trivalent metal oxide ratio of about100 to 1) then the yield of dimer decreases and the catalyst may tend todeactivate quickly. In certain embodiments, a content of trivalent metaloxide may be high (e.g., below a nickel oxide to trivalent metal oxideratio of about 4 to 1). A high trivalent metal oxide content may lowerthe yield of dimer. In some embodiments, a high trivalent metal oxidecontent may raise an average content of methyl branching in thedimerized olefin product. In certain embodiments, a content of trivalentmetal oxide may be such that the ratio of nickel oxide to trivalentmetal oxide falls within the range from about 4:1 to about 30:1. Inother embodiments, a content of trivalent metal oxide may be such thatthe ratio of nickel oxide to trivalent metal oxide is between about 5:1to about 20:1. In certain embodiments, a ratio of nickel oxide totrivalent metal oxide may be between about 8:1 to about 15:1.

In certain embodiments, a dimerization catalyst may contain from about21 percent to about 35 percent by weight of nickel oxide and about 1percent to about 5 percent by weight of trivalent metal oxide, based onthe total weight of nickel oxide, trivalent metal oxide and silica. Incertain embodiments, a dimerization catalyst may include from about 1.5percent to about 4 percent by weight trivalent metal oxide based on thetotal weight of nickel oxide, trivalent metal oxide and silica.

Preparation of dimerization catalysts are described in U.S. Pat. No.5,849, 972 to Vicari et al., entitled “Oligomerization Of Olefins ToHighly Linear Oligomers, and Catalyst For This Purpose,” and U.S. Pat.No. 5,169,824 to Saleh et al., entitled “Catalyst Comprising AmorphousNiO On Silica/Alumina Support,” both of which are fully incorporatedherein by reference.

Conversion of olefins in the first hydrocarbon feed stream to dimers indimerization unit 410, may be carried out as a batch, continuous (e.g.,using a fixed bed), semi-batch or multi-step process. In a batchprocess, the catalyst may be slurried with the first hydrocarbon feedstream. Temperature conditions for the dimerization reaction may rangefrom about 120° C. to about 200° C. In an embodiment, a reactiontemperature may range from about 150° C. to about 165° C. Reactiontemperatures may be controlled with evaporative cooling (e.g., theevaporation of lighter hydrocarbon fractions from the reaction mixturemay control the reaction temperature).

At least a portion of the produced dimerized olefins may be transportedto other processing units (e.g., an alkylation unit and hydroformylationunit) via second conduit 414. Produced dimerized olefins may includeolefins with an average carbon number from 8 to 18. In certainembodiments, produced dimerized olefins may include olefins with anaverage carbon number from 10 to 16. In some embodiments, produceddimerized olefins may include olefins with an average carbon number from10 to 14. In other embodiments, produced dimerized olefins may includeolefins with an average carbon number from 14 to 18.

Produced dimerized olefins may be separated, if desired, from thereaction mixture through techniques known in the art (e.g.,distillation, adsorption/desorption). In an embodiment, at least aportion of second hydrocarbon stream may exit dimerization unit 410 andenter separation unit 416 via conduit 418 as depicted in FIG. 8. Inseparation unit 416 the reaction mixture may be separated into aproduced dimerized olefins stream and a paraffins and unreacted olefinsstream through fractional distillation. The paraffins and unreactedolefins stream may contain hydrocarbons with a carbon number less than9. At least a portion of the paraffins and unreacted olefins stream maybe introduced into dimerization unit 410 via conduit 420. Produceddimerized olefins stream may exit separation unit 416 and be introducedinto second conduit 414 via conduit 422.

At least a portion of the second hydrocarbon stream may be transportedto hydroformylation unit 116 via second conduit 414. At least a portionof a third hydrocarbon stream may be introduced into second conduit 414via fourth conduit 424 to produce a combined hydrocarbon stream. Thecombined stream may enter hydroformylation unit 116. At least a portionof the olefins in the second hydrocarbon stream may be hydroformylatedin hydroformylation unit 116 to produce aliphatic alcohols. Thehydroformylation and subsequent purification steps may be performedunder conditions described for System 100.

As previously described for System 100, at least a portion of the thirdhydrocarbon stream may be used to regulate the olefin concentration inhydroformylation unit 116 at a concentration sufficient to maximizehydroformylation of the olefin. In addition, a third hydrocarbon streammay optimize the ratio of linear to branched aliphatic alcohols. Thethird hydrocarbon stream may be, but is not limited to, a hydrocarbonstream containing olefins, paraffins and/or hydrocarbon solvents.

In an embodiment, a third hydrocarbon stream may include olefins andparaffins. In certain embodiments, an average carbon number of thehydrocarbons in the third hydrocarbon stream ranges from 7 to 18. Insome embodiments, a paraffin content of the third hydrocarbon stream maybe between about 60 percent and about 90 percent by weight. In otherembodiments, a paraffin content of the third hydrocarbon stream may begreater than 90 percent by weight.

In an embodiment, an olefin content of a third hydrocarbon stream rangesbetween about 1 percent and about 99 percent relative to the totalhydrocarbon content. In certain embodiments, an olefin content of thethird hydrocarbon stream may be between about 45 percent and about 99percent by weight. In other embodiments, an olefin concentration of thethird hydrocarbon stream may be greater than 80 percent by weight.

The hydroformylation reaction mixture stream may enter separator 126 viathird conduit 128. In separator 126 at least two streams, bottom streamand a top stream may be produced. The bottom stream may be recycled backto hydroformylation unit 116 via recycle conduit 130. The top stream maybe purified and separated to produce at least two streams, a paraffinsand unreacted olefins stream and a crude aliphatic alcohol productstream. Methods used for purification and separation, in certainembodiments, may be the same as those described for System 100. Thecrude aliphatic alcohol product stream may be further purified to forman aliphatic alcohol product stream. The aliphatic alcohol productstream may include branched aliphatic alcohols (e.g., branched primaryalcohols). The aliphatic alcohol product stream may exit separator 126via product conduit 132 to be stored on site, sold commercially,transported off-site, and/or utilized in other processing units. Atleast a portion of the paraffins and unreacted olefins stream may exitseparator 126 and be recycled, combined with other process streams, sentto other processing units and/or be stored on site via fourth conduit134. In certain embodiments, a paraffins and unreacted olefins streammay be further separated into a hydrocarbons stream including paraffinsand unreacted olefins with a carbon number less than 9. The hydrocarbonstream including paraffins and unreacted olefins with a carbon numberless than 9 may be introduced upstream of and/or into the dimerizationunit.

In certain embodiments, a hydrocarbon stream from a dimerization unitmay be combined with a hydrocarbon stream from an isomerization unit toproduce a combined stream. The combined stream may be introduced into ahydroformylation unit. Combining streams from the two units may resultin a more economically valuable process to produce aliphatic alcohols. Afirst hydrocarbon stream, that includes paraffins and olefins may enterdimerization unit 410 via first conduit 412 as depicted for System 500,in FIG. 9. In an embodiment, a first hydrocarbon stream, may be producedfrom a Fischer-Tropsch process. An average carbon number of hydrocarbonsin a first hydrocarbon stream may range from 4 to 9. In certainembodiments, hydrocarbons in a first hydrocarbon stream may have anaverage carbon number range from 5 to 8. In some embodiments, an averagecarbon number of hydrocarbons in a first hydrocarbon stream may rangefrom 5 to 7. In other embodiments, an average carbon number ofhydrocarbons in a first hydrocarbon stream may range from 7 to 9.

In dimerization unit 410, at least a portion of the olefins may bedimerized as previously described for System 400. At least a portion ofthe dimerized olefins exit dimerization unit 410 as a second hydrocarbonstream. Depending on the choice of catalyst, the resulting dimer may bebranched. Branches of the olefin produced in dimerization unit 410 mayinclude methyl, ethyl and/or longer carbon chains. In an embodiment,produced dimerized olefins may contain greater than 50 percent methylbranches. In an alternate embodiment, produced dimerized olefins maycontain greater than 90 percent methyl branches. The average carbonnumber of produced dimerized olefins may range from 8 to 18. In someembodiments, an average carbon number of produced dimerized olefins mayrange from 10 to 16. In certain embodiments, an average carbon number ofproduced dimerized olefins may range from 10 to 14. In otherembodiments, an average carbon number of produced dimerized olefins mayrange from 14 to 18. Produced dimerized olefins may be separated fromthe reactor product using generally known techniques (e.g., fractionaldistillation). In an embodiment, produced dimerized olefins may beseparated from the reaction mixture and processed as previouslydescribed for System 400. ¹H NMR analysis of the composition anddetermination of the branching of the dimerized olefins may beperformed. The second hydrocarbon stream may be transferred to otherprocessing units, (e.g., separation units, alkylation units,hydroformylation units) or to storage units through a conduit.

At least a portion of the second hydrocarbon stream may exitdimerization unit 410 and enter hydroformylation unit 116 via secondconduit 414. A fourth hydrocarbon stream may be introduced directly intohydroformylation unit 116 through one or more hydroformylation unitports. At least a portion of a fourth hydrocarbon stream may beintroduced into second conduit 414 via fifth conduit 512 upstream ofhydroformylation unit 116 to produce a combined stream. The fourthhydrocarbon stream may be a stream exiting from isomerization unit 514.

Isomerization unit 514 may be fed by a third hydrocarbon streamcontaining paraffins and unreacted olefins via a sixth conduit 516. Inisomerization unit 514, at least a portion of the olefins in the thirdhydrocarbon stream may be isomerized to branched olefins to produce thefourth hydrocarbon stream. A third hydrocarbon stream may includehydrocarbons with an average carbon number from 7 to 18. In certainembodiments, a third hydrocarbon stream may include hydrocarbons with anaverage carbon number from 10 to 17. In some embodiments, a thirdhydrocarbon stream may include hydrocarbons with an average carbonnumber from 10 to 13. In other embodiments, a third hydrocarbon streammay include hydrocarbons with an average carbon number from 14 to 17. Insome embodiments, a third hydrocarbon stream includes alpha-olefins. Incertain embodiments, a third hydrocarbon stream is a stream derived froma Fischer-Tropsch process. The alpha-olefin content of the thirdhydrocarbon stream may be greater than 70 percent of the total amount ofolefins in the third hydrocarbon stream. In isomerization unit 514, atleast a portion of the olefins in the third hydrocarbon stream may beisomerized to branched olefins (e.g., isoolefins) to produce a fourthhydrocarbon stream.

In certain embodiments, isomerization unit 514 may have several pointsof entry to accommodate process streams, which may vary in composition.Process streams may be from other processing units and/or storage units.Examples of process streams include, but are not limited to, a diluenthydrocarbon stream, and/or other hydrocarbon streams that includeolefins and paraffins derived from other processes. As used herein,“entry into the isomerization unit” refers to entry of process streamsinto the isomerization unit through one or more entry points.

Conditions for olefin isomerization in isomerization unit 514 may becontrolled such that the number of carbon atoms in the olefins beforeand after the isomerization is substantially the same. U.S. Pat. No.5,648,584 to Murray, entitled “Process for Isomerizing Linear Olefins toIsoolefins” and U.S. Pat. No. 5,648,585 to Murray et al., entitled“Process for Isomerizing Linear Olefins to Isoolefins,” both of whichare incorporated herein by reference; describe catalysts and processconditions to skeletally isomerize linear olefins to branched olefins.

In an embodiment, linear olefins in a third hydrocarbon stream areisomerized in isomerization unit 514 by contacting at least a portion ofthe third hydrocarbon stream with a zeolite catalyst. The zeolitecatalyst may have at least one channel with a crystallographic freechannel diameter ranging from greater than 4.2 Å and less than 7 Å. Thezeolite catalyst may have an elliptical pore size large enough to permitentry of a linear olefin and diffusion, at least partially, of abranched olefin. The pore size of the zeolite catalyst may also be smallenough to retard coke formation.

Temperatures at which the olefin isomerization may be conducted inisomerization unit 514 range from about 200° C. to about 500° C.Temperatures in isomerization unit 514 are, in some embodiments, keptbelow the temperature at which the olefin will crack extensively. Asused herein, “cracking” refers to the process of thermally degradingmolecules into smaller molecules. To inhibit cracking, low temperaturesmay be used at low feed rates. In certain embodiments, lowertemperatures may be used when the amount of oxygenates present in theprocess stream is low. Higher feed rates may be desirable to increasethe production rate of isomerised products. Higher feed rates may beused, in some embodiments, when operating at higher reactiontemperatures. The reaction temperature, however, should be set such thatcracking to lower boiling weight products is minimized. For example,greater than 90 percent of linear C₁₂-C₁₄ olefins may be converted tobranched olefins at 230° C. at a feed rate of 60 grams per hour per 6grams of catalyst with minimal cracking. Pressures maintained inisomerization unit 514 may be at a hydrocarbon partial pressure rangingfrom about 0.1 atmospheres (10 kPa) to about 20 atmospheres (2026 kPa).In an embodiment, a partial pressure may range from above about 0.5atmospheres (51 kPa) to about 10 atmospheres (1013 kPa).

The fourth hydrocarbon stream may be combined with the secondhydrocarbon stream in second conduit 414. Hydrocarbons in the fourthhydrocarbon stream may have an average carbon number from 7 to 18. Incertain embodiments, hydrocarbons in the fourth hydrocarbon stream mayhave an average carbon number from 10 to 17. In some embodiments,hydrocarbons in the fourth hydrocarbon stream may have an average carbonnumber from 10 to 13. In other embodiments, an average carbon number ofthe hydrocarbons in a feed stream may range from 14 to 17.

In an embodiment, a fifth hydrocarbon stream may be introduced intohydroformylation unit 116 through one or more hydroformylation ports. Incertain embodiments, at least a portion of a fifth hydrocarbon streammay be introduced into second conduit 414 upstream of hydroformylationunit 116 via seventh conduit 518 to produce a combined stream. Thecombined stream may enter hydroformylation unit 116 and at least aportion of the olefins in the combined stream may be hydroformylated toproduce a hydroformylation reaction stream.

Hydroformylation reaction conditions may be the same as previouslydescribed for System 100. Separation of the hydroformylation reactionstream into at least two streams, a bottom stream and a top stream, maybe performed as previously described for System 100. The bottom streammay be recycled to the hydroformylation unit, in certain embodiments.The top stream may be further purified and separated into at least twostreams, a paraffins and unreacted olefins stream and a crude aliphaticalcohol product stream, using techniques generally known. In certainembodiments, techniques used for purification and separation of a topstream may be the same as those described for System 100. The crudealiphatic alcohol product stream may be further purified to produce analiphatic alcohol product stream using techniques previously describedfor System 100. The aliphatic alcohols in the aliphatic alcohol productstream may be branched aliphatic alcohols.

The fourth and fifth hydrocarbon streams may be used to regulate theolefin concentration in hydroformylation unit 116 at a concentrationsufficient to maximize hydroformylation of the olefin. The fourth andfifth hydrocarbon streams may be, but are not limited to, a hydrocarbonstream containing olefin, paraffins and/or hydrocarbon solvents. In anembodiment, a paraffin content of the fourth and fifth hydrocarbonstreams may be greater than 50 percent and less than 99 percent relativeto the total hydrocarbon content. In certain embodiments, a paraffincontent of the fourth and fifth hydrocarbon streams may be between about60 percent and about 90 percent relative to the total hydrocarboncontent. In other embodiments, a paraffin content may be greater than 90percent relative to the total hydrocarbon content.

In an embodiment, an olefin content of a fifth hydrocarbon stream rangesbetween about 1 percent and about 99 percent relative to the totalhydrocarbon content. In certain embodiments, an olefin content of afifth hydrocarbon stream ranges between about 45 percent and about 95percent. In other embodiments, an olefin content of a fifth hydrocarbonstream may be greater than 80 percent relative to the total hydrocarbonstream.

A combined stream may include, but is not limited to, a secondhydrocarbon stream, a fourth hydrocarbon stream, a fifth hydrocarbonstream and/or combinations thereof, may be introduced intohydroformylation unit 116 via second conduit 414. An advantage ofcombining the streams may be that overall production of aliphaticalcohols may be increased with fewer throughputs. At least a portion ofthe olefins in the combined stream may be hydroformylated underconditions previously described for System 100 to produce aliphaticalcohols. An average carbon number of the alcohols produced inhydroformylation unit 116 may be less than 20. In certain embodiments,an average carbon number of alcohols produced in hydroformylation unit116 may range from 7 to 19. In some embodiments, an average number ofalcohols produced in hydroformylation unit 116 may range from 10 to 18.In other embodiments, an average number of alcohols produced in ahydroformylation unit 116 may range from 14 to 19.

The hydroformylation reaction mixture stream may enter separator 126 viathird conduit 128. Separation of the aliphatic alcohol product from atleast a portion of the hydroformylation reaction stream may be performedin separation unit 126. The separation may produce at least two streams,a bottom stream and a top stream using generally known techniques (e.g.,distillation). At least a portion of the bottom stream may be recycledto hydroformylation unit 116 via recycle conduit 130. The top stream maybe further purified and separated to produce at least two streams, aparaffins and unreacted olefins stream and a crude aliphatic alcoholproduct stream using techniques previously described for System 100. Atleast a portion of the crude aliphatic alcohol product stream may befurther purified to produce an aliphatic alcohol product stream usinggenerally known techniques. The aliphatic alcohol product stream mayexit separation unit 126 and be transported via product conduit 132 tobe stored on site, sold commercially, transported off-site, and/orutilized in other processing units.

At least a portion of the paraffins and unreacted olefins stream mayexit separation unit 126 and be transported via fourth conduit 134 toanother processing unit, and/or storage vessel. In certain embodiments,a paraffins and unreacted olefins stream may be further separated into ahydrocarbons stream including paraffins and unreacted olefins with acarbon number less than 8. The hydrocarbon stream including paraffinsand unreacted olefins with a carbon number less than 8 may be introducedupstream of the dimerization unit and/or into the dimerization unit.

In certain embodiments, to reduce production costs of producing branchedaliphatic alcohols, a stream containing a significant amount ofparaffins and a minor amount of olefins may first be isomerized thenhydroformylated to form branched aliphatic alcohols. Processing a streamcontaining a minor amount of olefins through an isomerization unit priorto hydroformylation may save production time, dehydrogenation catalystcost and/or enhance the overall economic viability of the stream. Insome embodiments, after hydroformylation, paraffins and unreactedolefins may be recycled to a dehydrogenation unit to produce a streamenriched in olefins. The enriched olefins stream may be recycled into anisomerization unit.

Referring to System 600 in FIG. 10, a first hydrocarbon stream may beintroduced into isomerization unit 514 via first conduit 610. Inisomerization unit 514, at least a portion of the olefins in the firsthydrocarbon stream may be isomerized to branched olefins to produce asecond hydrocarbon stream. A first hydrocarbon stream may includehydrocarbons with an average carbon number from 7 to 18. In certainembodiments, a first hydrocarbon stream may include hydrocarbons with anaverage carbon number from 10 to 17. In some embodiments, a firsthydrocarbon stream may include hydrocarbons with an average carbonnumber from 10 to 17. In other embodiments, a first hydrocarbon streammay include hydrocarbons with an average carbon number from 14 to 17. Afirst hydrocarbon stream may be a stream derived from a Fischer-Tropschprocess. A first hydrocarbon stream includes alpha-olefins, in someembodiments. The alpha-olefin content of the first hydrocarbon streammay be greater than 70 percent of the total amount of olefins in thefirst hydrocarbon stream. In isomerization unit 514, at least a portionof the olefins in the first hydrocarbon stream may be isomerized tobranched olefins (e.g., isoolefins) to produce a second hydrocarbonstream.

Conditions for olefin isomerization in isomerization unit 514 may becontrolled such that the number of carbon atoms in the olefins beforeand after the isomerization is substantially the same. U.S. Pat. No.5,648,584 to Murray, entitled “Process for Isomerizing Linear Olefins toIsoolefins” and U.S. Pat. No. 5,648,585 to Murray et al., entitled“Process for Isomerizing Linear Olefins to Isoolefins,” both of whichare incorporated herein by reference; describe catalysts and processconditions to skeletally isomerize linear olefins to branched olefins.

In an embodiment, linear olefins in a first hydrocarbon stream areisomerized in isomerization unit 514 by contacting at least a portion ofthe first hydrocarbon stream with a zeolite catalyst. The zeolitecatalyst may have at least one channel with a crystallographic freechannel diameter ranging from greater than 4.2 Å and less than 7 Å. Thezeolite catalyst may have an elliptical pore size large enough to permitentry of a linear olefin and diffusion, at least partially, of abranched olefin. The pore size of the zeolite catalyst may also be smallenough to retard coke formation.

Temperatures at which the olefin isomerization may be conducted rangefrom about 200° C. to about 500° C. Temperatures in isomerization unit514 are, in some embodiments, kept below the temperature at which theolefin will crack extensively. To inhibit cracking, low temperatures maybe used at low feed rates. In certain embodiments, lower temperaturesmay be used when the amount of oxygenates present in the process streamis low. Higher feed rates may be desirable to increase the productionrate of isomerised products. Higher feed rates may be used, in someembodiments, when operating at higher reaction temperatures. Thereaction temperature, however, should be set such that cracking to lowerboiling weight products is minimized. For example, greater than 90percent of linear olefins may be converted to branched olefins at 230°C. at a feed rate of 60 grams per hour per 6 grams of catalyst withminimal cracking. Pressures maintained in isomerization unit 514 may beat a hydrocarbon partial pressure ranging from about 0.1 atmosphere (10kPa) to about 20 atmospheres (2026 kPa). In an embodiment, partialpressure may range from above about 0.5 atmosphere (51 kPa) to about 10atmospheres (1013 kPa).

The branched olefin produced in isomerization unit 514 may includemethyl, ethyl and/or longer carbon chain branches. The isomerized olefincomposition may be analyzed by ¹H NMR as previously described for System100.

Isomerization unit 514 may produce a second hydrocarbon stream thatincludes olefins and paraffins. At least a portion of the secondhydrocarbon stream contains branched olefins. The second hydrocarbonstream may exit isomerization unit 514 via second conduit 612 and beintroduced into hydroformylation unit 116. At least a portion of theolefins in the second hydrocarbon stream may be hydroformylated underconditions previously described for System 100 to produce aliphaticalcohols.

In an embodiment, olefins may be separated, if desired, from the secondhydrocarbon stream through techniques generally known in the art (e.g.,distillation, molecular sieves, extraction, adsorption,adsorption/desorption, and/or membranes). Referring to FIG. 11, a secondhydrocarbon stream may exit isomerization unit 514 and enter separationunit 118 via separation conduit 614. Separation unit 118 may produce atleast two streams, a branched olefins stream and a linear olefins andparaffins stream. In separation unit 118, the second hydrocarbon streammay be contacted with molecular sieves (e.g., zeolite or urea) of thecorrect pore size for absorption of branched olefins and/or linearolefins and paraffins. Subsequent desorption of at least a portion ofthe branched olefins and/or at least a portion of the linear olefins andparaffins from the molecular sieves may produce at least two streams, abranched olefins stream and a linear olefins and paraffins stream.

Separation unit 118 may include a fixed bed containing adsorbent forseparation of the second hydrocarbon stream to produce a branched olefinstream and a linear olefins and paraffins stream. Separationtemperatures in separation unit 118 may range from about 100° C. toabout 400° C. In some embodiments, separation temperatures may rangefrom 180° C. to about 380° C. Separations in separation unit 118 may beconducted at a pressure ranging from about 2 atmospheres (202 kPa) toabout 7 atmospheres (710 kPa). In some embodiments, a pretreatment of asecond hydrocarbon stream may be performed to prevent adsorbentpoisoning.

At least a portion of the linear olefins and paraffins stream may berecycled, transported to other processing units and/or stored on site.In an embodiment, at least a portion of the linear olefins and paraffinsstream may be combined with first hydrocarbon stream in first conduit610 via linear olefin and paraffin recycle conduit 616. The combinedstream may enter isomerization unit 514 via first conduit 610 tocontinue the process to produce isomerized olefins. In some embodiments,a linear olefins and paraffins stream may be introduced directly intoisomerization unit 514. In some embodiments, a linear olefins andparaffins stream may be introduced into dehydrogenation unit 618.

At least a portion of the branched olefins stream may be transported andutilized in other processing streams and/or stored on site via branchedolefins conduit 620. In some embodiments, at least a portion of abranched olefins stream may exit separation unit 118 and be combinedwith second hydrocarbon stream in second conduit 612 upstream ofhydroformylation unit 116 via branched olefins conduit 620. In otherembodiments, at least a portion of a branched olefins stream may exitseparation unit 118 and be introduced directly into a hydroformylationunit.

Referring to FIG. 10, the second hydrocarbon stream may exitisomerization unit 514 and via second conduit 612 and enterhydroformylation unit 116. Hydroformylation reaction conditions may bethe same as previously described for System 100. Separation of thehydroformylation reaction stream into at least two streams, a bottomstream and a top stream, may be performed as previously described forSystem 100. The bottom stream may be recycled to the hydroformylationunit, in certain embodiments. The top stream may be further purified andseparated into at least two streams, a paraffins and unreacted olefinsstream and a crude aliphatic alcohol product stream, using techniquesgenerally known. In certain embodiments, techniques used to purificationand separation atop stream may be the same as those described for System100. The crude aliphatic alcohol product stream may be further purifiedto produce an aliphatic alcohol product stream using techniquespreviously described for System 100. The aliphatic alcohols in thealiphatic alcohol product stream may be branched aliphatic alcohols.

In some embodiments, a third hydrocarbon stream may be used to regulatethe olefin concentration in hydroformylation unit 116 at a concentrationsufficient to maximize hydroformylation of the olefin. The thirdhydrocarbon streams may be, but is not limited to, a hydrocarbon streamcontaining olefin, paraffins and/or hydrocarbon solvents. In anembodiment, a third hydrocarbon stream may include olefins andparaffins. In certain embodiments, an average carbon number of thehydrocarbons in the third hydrocarbon stream ranges from 7 to 18. Insome embodiments, a paraffin content of the third hydrocarbon stream maybe between about 60 percent and about 90 percent by weight. In otherembodiments, a paraffin content of the third hydrocarbon stream may begreater than 90 percent by weight.

In an embodiment, an olefin content of a third hydrocarbon stream rangesbetween about 1 percent and about 99 percent relative to the totalhydrocarbon content. In certain embodiments, an olefin content of thethird hydrocarbon stream may be between about 45 percent and about 99percent by weight. In other embodiments, an olefin concentration of thethird hydrocarbon stream may be greater than 80 percent by weight.

The hydroformylation reaction mixture stream may enter separator 126 viathird conduit 128. Separation of the aliphatic alcohol product from atleast a portion of the hydroformylation reaction stream may be performedin separation unit 126. The separation may produce at least two streams,a bottom stream and a top stream, using generally known techniques(e.g., distillation). At least a portion of the bottom stream may berecycled to hydroformylation unit 116 via recycle conduit 130. The topstream may be further purified and separated to produce at least twostreams, a paraffins and unreacted olefins stream and a crude aliphaticalcohol product stream using techniques previously described for System100. At least a portion of the crude aliphatic alcohol product streammay be further purified to produce an aliphatic alcohol product streamusing generally known techniques. The aliphatic alcohol product streammay exit separation unit 126 and be transported via product conduit 132to be stored on site, sold commercially, transported off-site, and/orutilized in other processing units.

At least a portion of the paraffins and unreacted olefins stream mayexit separation unit 126 and be transported via fourth conduit 134 toanother processing unit, and/or storage vessel. At least a portion ofthe separated paraffins and unreacted olefins may enter dehydrogenationunit 618 via fourth conduit 134. An average carbon number of thehydrocarbons in the paraffins and unreacted olefins stream may rangefrom 7 to 18. In certain embodiments, an average carbon number of theparaffins and unreacted olefins stream may range from 10 to 17. In someembodiments, an average carbon number of the paraffins and unreactedolefins stream may range from 10 to 13. In other embodiments, an averagecarbon number of the hydrocarbons in the paraffins and unreacted olefinsstream may range from 14 to 17.

In an embodiment, at least a portion of the paraffins and unreactedolefins stream may be introduced into dehydrogenation unit 618 viafourth conduit 134. At least a portion of the unreacted paraffins in thehydrocarbon stream may be dehydrogenated to produce an olefinichydrocarbon stream by use of a catalyst selected from a wide range ofcatalyst types. For example, the catalyst may be based on a metal and/ora metal compound deposited on a porous support. The metal or metalcompound may include, but is not limited to, chrome oxide, iron oxideand noble metals.

Techniques of preparing catalysts, for performing the dehydrogenationstep and for performing associated separation steps are generally known.For example, suitable procedures for preparing catalysts and performingthe dehydrogenation step are described in U.S. Pat. No. 5,012,021 toVora et al., entitled “Process For the Production of Alkyl AromaticHydrocarbons Using Solid Catalysts;” U.S. Pat. No. 3,274,287 to Moore etal., entitled “Hydrocarbon Conversion Process and Catalyst;” U.S. Pat.No. 3,315,007 to Abell et al., entitled “Dehydrogenation of SaturatedHydrocarbons Over Noble-Metal Catalyst;” U.S. Pat. No. 3,315,008 toAbell et al., entitled “Dehydrogenation of Saturated Hydrocarbons OverNoble-Metal Catalyst;” U.S. Pat. No. 3,745,112 to Rausch, entitled“Platinum-Tin Uniformly Dispersed Hydrocarbon Conversion Catalyst andProcess;” U.S. Pat. No. 4,506,032 to Imai et al., entitled“Dehydrogenation Catalyst Composition” and U.S. Pat. No. 4,430,517 toImai et al., entitled “Dehydrogenation Process Using a CatalyticComposition,” all of which are incorporated by reference herein.

Reaction conditions in dehydrogenation unit 618 may be varied to controlunwanted side products (e.g., coke, dienes oligomers, cyclizedhydrocarbons) and control double bond position in the olefin. In certainembodiments, temperatures may range from greater than 300° C. to lessthan 700° C. In other embodiments, a dehydrogenation reactiontemperature may range from about 450° C. to about 550° C. Duringdehydrogenation, pressures in dehydrogenation unit 618 may range fromgreater than 0.010 atmosphere (1 kPa) to about 25.0 atmospheres (2534kPa). In an embodiment, a total pressure of dehydrogenation unit 618during the reaction may range from about 0.10 atmosphere (10 kPa) toabout 15.0 atmospheres (15200 kPa). In certain embodiments, pressure indehydrogenation unit 618 may range from about 1.0 atmosphere (101 kPa)to about 5.0 atmospheres (510 kPa). In order to prevent coke fromforming, hydrogen may be fed into dehydrogenation unit 618 together withthe paraffins and unreacted olefins stream. The hydrogen to paraffinsmolar ratio may be set between about 0.1 moles of hydrogen to about 20moles of paraffins. In some embodiments, a hydrogen to paraffin molarratio is about 1 to 10.

The amount of time (e.g., the residence time) that a process streamremains in dehydrogenation unit 618 may determine, to some extent, theamount of olefins produced. Generally, the longer a process streamremains in dehydrogenation unit 618, the conversion level of paraffinsto olefins increases until an olefin-paraffin thermodynamic equilibriumis obtained. Residence time of the paraffins and unreacted olefinsstream in dehydrogenation unit 618 may be such that the conversion levelof paraffins to olefins may be kept below 50 mole percent. In certainembodiments, conversion level of paraffins to olefins may be kept in therange of from 5 to 30 mole percent. By keeping the conversion level low,side reactions may be prevented (e.g., diene formation and cyclizationreactions).

Dehydrogenation unit 618 receives at least a portion of the paraffinsand unreacted olefins stream from separation unit 126 and produces anolefinic hydrocarbon stream. The olefinic hydrocarbon stream may includeparaffins. The concentration of the olefins in the olefinic hydrocarbonstream may be between 5 and 50 percent by weight. In certainembodiments, a concentration of olefins may range from 10 to 20 percentby weight. The olefins produced in dehydrogenation unit 618 may bepredominately linear olefins. The average carbon number of thehydrocarbons in the olefinic stream may range from 7 to 18. The averagecarbon number of the hydrocarbons in the olefinic stream ranges, incertain embodiments, from about 10 to 17. In some embodiments,hydrocarbons in the olefinic stream may have an average carbon numberfrom 10 to 13. In other embodiments, an average carbon number of thehydrocarbons in the olefinic stream may range from 14 to 17.

In certain embodiments, at least a portion of non-converted paraffinsmay be separated from the olefinic stream and, if desired, thenon-converted paraffins may be recycled to dehydrogenation unit 618 toundergo dehydrogenation. Such separation may be accomplished byextraction, distillation or adsorption techniques.

In some embodiments, at least a portion of a paraffinic hydrocarbonstream may be introduced upstream of dehydrogenation unit 618 to producea combined stream. The combined stream may enter dehydrogenation unit618 to undergo dehydrogenation. In other embodiments, a paraffinichydrocarbon stream is introduced directly into dehydrogenation unit 618through one or more points of entry.

The olefinic hydrocarbon stream may be combined with first hydrocarbonstream in first conduit 610 of isomerization unit 514 via fifth conduit622. The combined stream may enter isomerization unit 514 and at least aportion of the olefins present in the combined stream may be isomerizedto branched olefins. In some embodiments, an olefinic hydrocarbon streammay exit dehydrogenation unit 618 and be directly introduced intoisomerization unit 514 through one or more points of entry.

In certain embodiments, additional hydrocarbon streams may be usedcontrol reaction conditions and/or optimize the concentration ofparaffins and unreacted olefins in isomerization unit 514,hydroformylation unit 116 and/or other processing units used to producealiphatic alcohols. Referring to FIG. 12, a first hydrocarbon stream maybe introduced into isomerization unit 514 via first conduit 610. Thefirst hydrocarbon stream may include olefins and paraffins. In certainembodiments, hydrocarbons in the first hydrocarbon stream may have anaverage carbon number from 7 to 18. In certain embodiments, hydrocarbonsin the first hydrocarbon stream may have an average carbon number from10 to 17. In some embodiments, an average carbon number of thehydrocarbons in a feed stream may range from 10 to 13. In otherembodiments, an average carbon number of the hydrocarbons in a feedstream may range from 14 to 17. Olefins may, in some embodiments, bealpha-olefins. The alpha-olefin content of the first hydrocarbon streammay be greater than 70 percent of the total amount of olefins in thefirst hydrocarbon stream. In certain embodiments, a first hydrocarbonstream is derived from a Fischer-Tropsch process. In isomerization unit514, at least a portion of the olefins in the first hydrocarbon streammay be isomerized to branched olefins to produce a second hydrocarbonstream. Conditions of the olefin isomerization may be controlled, aspreviously described for System 600, such that the number of carbonatoms in the olefin prior to and subsequent to the isomerizationconditions is substantially the same.

At least a portion of a paraffinic hydrocarbon stream may be introducedinto first conduit 610 via sixth conduit 624 upstream of isomerizationunit 514 to produce a combined stream. The combined stream may enterisomerization unit 514 via first conduit 610. In other embodiments, aparaffinic hydrocarbon stream is introduced directly into isomerizationunit 514 through one or more points of entry.

At least a portion of the olefins in the combined stream may beisomerized to branched olefins in isomerization unit 514 to produce asecond hydrocarbon stream. Addition of the paraffinic hydrocarbon streammay be used to optimize the olefin concentration in isomerization unit514 and to control the extent of branching in the produced olefins.Concentration of paraffins in the paraffinic hydrocarbon stream may bebetween about 10 percent and about 99 percent by weight. In certainembodiments, a paraffin concentration may range between about 10 percentand about 50 percent by weight. In some embodiments, a paraffinconcentration may range between about 25 percent and about 75 percent byweight. In other embodiments, a paraffinic stream may include olefins.An olefin concentration in the hydrocarbon stream may be between 20 and80 percent.

The second hydrocarbon stream may exit isomerization unit 514 and beintroduced into hydroformylation unit 116 via second conduit 612. Thesecond hydrocarbon stream may include branched olefins. At least aportion of a third hydrocarbon stream may be introduced into secondconduit 612 via seventh conduit 626 upstream of hydroformylation unit116 to form a mixed stream. The mixed stream may be then introduced intohydroformylation unit 116 via second conduit 612. At least a portion ofthe olefins in the mixed stream may be hydroformylated using processconditions as previously described for System 100. In some embodiments,a third hydrocarbon stream may be introduced directly intohydroformylation unit 116 through one or more points of entry. It shouldbe understood that an olefin concentration in the process streams may beadjusted by adding a stream through sixth conduit 624 only, seventhconduit 626 only, directly into hydroformylation unit 116 only or bycombinations thereof.

The third hydrocarbon stream in conduit 626 may be used to optimize theolefin concentration in hydroformylation unit 116 to maximizehydroformylation of the olefins. The third hydrocarbon stream may befrom the same source as the first hydrocarbon stream. Alternatively, thethird hydrocarbon stream may be a hydrocarbon stream that includesolefins, paraffins, and/or hydrocarbon solvents derived from anothersource.

The third hydrocarbon stream may include olefins and paraffins. Incertain embodiments, an average carbon number of the hydrocarbons in thethird hydrocarbon stream ranges from 7 to 18. In certain embodiments, athird hydrocarbon stream may include olefins and paraffins. In someembodiments, a paraffin content of the third hydrocarbon stream may bebetween about 60 percent and about 90 percent by weight. In otherembodiments, a paraffin content of the third hydrocarbon stream may begreater than 90 percent by weight.

In an embodiment, an olefin content of a third hydrocarbon stream rangesbetween about 1 percent and about 99 percent relative to the totalhydrocarbon content. In certain embodiments, an olefin content of thethird hydrocarbon stream may be between about 45 percent and about 99percent by weight. In other embodiments, an olefin concentration of thethird hydrocarbon stream may be greater than 80 percent by weight.

In some embodiments, a third hydrocarbon stream may include linearolefins. Addition of a stream that includes linear olefins downstreamfrom the isomerization unit allows the creation of a hydroformylationfeed stream that includes a mixture of linear and branched olefins. Byintroducing a stream including branched and linear olefins intohydroformylation unit 116 a mixture of branched and linear aliphaticalcohol products may be obtained. Varying the amount of linear olefinsadded to the hydroformylation feed stream may control the ratio oflinear to branched aliphatic alcohol products. A mixture of branched andlinear aliphatic alcohols may have improved properties when converted tosurfactants or other products. Examples of improved surfactantproperties include, but are not limited to, low skin and eye irritation,foaming properties, biodegradability, cold-water solubility andcold-water detergency. Applications for these surfactants include, butare not limited to, personal care products, household and industriallaundry products, hand dishwashing products, machine lubricant additivesand lubricating oil formulations.

The hydroformylation reaction mixture stream may enter separator 126 viathird conduit 128. Separation of the aliphatic alcohol product from atleast a portion of the hydroformylation reaction stream may be performedin separation unit 126. The separation may produce at least two streams,a bottom stream and a top stream using generally known techniques (e.g.,distillation). At least a portion of the bottom stream may be recycledto hydroformylation unit 116 via recycle conduit 130. The top stream maybe further purified and separated to produce at least two streams, aparaffins and unreacted olefins stream and a crude aliphatic alcoholproduct stream using techniques previously described for System 100. Atleast a portion of the crude aliphatic alcohol product stream may befurther purified to produce an aliphatic alcohol product stream usinggenerally known techniques. The aliphatic alcohol product stream mayexit separation unit 126 and be transported via product conduit 132 tobe stored on site, sold commercially, transported off-site, and/orutilized in other processing units. Produced aliphatic alcohols in thealiphatic alcohol product stream may have an average carbon number from8 to 19. In certain embodiments, produced aliphatic alcohols in thealiphatic alcohol product stream may have an average carbon number from11 to 18. In some embodiments, produced aliphatic alcohols in thealiphatic alcohol product stream may have an average carbon number from11 to 14. In other embodiments, produced aliphatic alcohols in thealiphatic alcohol product stream may have an average carbon number from15 to 18.

At least a portion of the paraffins and unreacted olefins stream mayexit separation unit 126 and be transported via fourth conduit 134 toanother processing unit, and/or storage vessel. At least a portion ofthe separated paraffins and unreacted olefins may enter dehydrogenationunit 620 via fourth conduit 134. An average carbon number of thehydrocarbons in the paraffins and unreacted olefins stream may rangefrom 7 to 18. In certain embodiments, an average carbon number of theparaffins and unreacted olefins stream may range from 10 to 17. In someembodiments, an average carbon number of the paraffins and unreactedolefins stream may range from 10 to 13. In other embodiments, an averagecarbon number of the hydrocarbons in the paraffins and unreacted olefinsstream may range from 14 to 17.

At least a portion of the paraffins in the hydrocarbon stream may bedehydrogenated using process conditions as previously described. Atleast a portion of the resulting olefinic hydrocarbon stream may exitdehydrogenation unit 618 and be transported to another processing unitand/or a storage vessel via fifth conduit 622.

At least a portion of a paraffinic hydrocarbon stream may be introducedinto fourth conduit 134 via eighth conduit 628 upstream ofdehydrogenation unit 618 to produce a combined stream. The combinedstream may enter dehydrogenation unit 618 via fourth conduit 134. Inother embodiments, a paraffinic hydrocarbon stream is introduceddirectly into dehydrogenation unit 618 through one or more points ofentry.

In certain embodiments, at least a portion of non-converted paraffinsmay be separated from dehydrogenated compounds in the olefinic stream.Such separation may be accomplished by extraction, distillation or,adsorption techniques. At least a portion of the non-converted paraffinsmay be recycled to dehydrogenation unit 618 to undergo furtherdehydrogenation.

At least a portion of the olefinic hydrocarbon stream may exitdehydrogenation unit 618 via fifth conduit 622 and be combined with thefirst hydrocarbon stream in first conduit 610 upstream of isomerizationunit 514 to produce a combined stream. The combined stream may beintroduced into isomerization unit 514 via first conduit 610 and atleast a portion of the olefins in the combined stream may be isomerizedto branched olefins. In some embodiments, an olefinic hydrocarbon streammay be introduced directly into isomerization unit 514 via one or morepoints of entry. Alternatively, at least a portion of the olefinichydrocarbon stream may be combined with a second hydrocarbon stream insecond conduit 612 downstream of isomerization unit 514 to produce amixed stream. Depending on the dehydrogenation conditions, the mixedstream may include linear olefins. Addition of the olefinic hydrocarbonstream with the second hydrocarbon stream may produce a mixed streamthat includes both linear and branched olefins.

In certain embodiments, a first hydrocarbon stream may contain unwantedcompounds (e.g., oxygenates and dienes) that may reduce catalystselectivity in processes used to produce aliphatic alcohols. Removal ofthe unwanted compounds may be performed by hydrogenation of the firsthydrocarbon stream. Hydrogenation of the first hydrocarbon stream, incertain embodiments, may produce a hydrocarbon stream that includesgreater than 90 percent paraffins. The hydrogenated hydrocarbon streammay be dehydrogenated to produce an olefinic stream. The catalyst usedin the dehydrogenation process may control the position of the olefindouble bond. In certain embodiments, an olefinic hydrocarbon stream mayinclude olefins in which greater than 70 percent of the olefins arealpha-olefins of a linear carbon skeletal structure. In otherembodiments, an olefinic hydrocarbon stream may include olefins in which50 percent or more of the olefin molecules present may be internalolefins.

A first hydrocarbon stream may be introduced into hydrogenation unit 710via first conduit 712 as depicted for System 700, in FIG. 13.Hydrocarbons in the first hydrocarbon stream may have an average carbonnumber from 7 to 18. In certain embodiments, hydrocarbons in the firsthydrocarbon stream may have an average carbon number from 10 to 17. Insome embodiments, hydrocarbons in the first hydrocarbon stream may havean average carbon number from 10 to 13. In other embodiments, an averagecarbon number of the hydrocarbons in a feed stream may range from 14 to17. The first hydrocarbon stream includes olefins and paraffins. Inhydrogenation unit 710, at least a portion of the olefins in the firsthydrocarbon stream may be hydrogenated to paraffins to produce a secondhydrocarbon stream.

Reaction conditions in hydrogenation unit 710 may be controlled tohydrogenate olefins and dienes and to remove oxygenates. An operatingtemperature of hydrogenation unit 710 may range between about 100° C.and about 300° C. In some embodiments, an operating temperature mayrange between about 150° C. and about 275° C. In other embodiments, anoperating temperature may range between about 175° C. and 250° C. Anoperating pressure may range from about 5 atmospheres (506 kPa) to about150 atmospheres (1520 kPa). In some embodiments, an operating pressuremay range from 10 atmospheres psi (1013 kPa) to about 50 atmospheres(5065 kPa).

Hydrogenation processes may be carried out using any type of catalystbed arrangement (e.g., fluidized bed, moving bed, slurry phase bed or afixed bed). In certain embodiments, a fixed bed arrangement may be used.In a fixed bed system, hydrogen may be supplied to the hydrogenationstage at a gas hourly space velocity in the range from about 100 normalliter gas/liter catalyst/hour (NL/L/hr) to about 1000 NL/L/hr. In someembodiments, hydrogen may be supplied at a gas hourly space velocity inthe range from about 250 NL/L/hr to 5000 NL/L/hr. “Gas space velocity asexpressed in units of normal liter of gas/liter of catalyst/hour,” asused herein, is the volume of a gas in liters at standard conditions of0° C. and 760 mm Hg.

Hydrogenation catalysts are generally known and are commerciallyavailable in a large variety of compositions. In some embodiments, ahydrogenation catalyst may include one or more metals from Groups VIBand VII of the periodic Table of the Elements. In certain embodiments,metals may include, but are not limited to, molybdenum, tungsten,cobalt, nickel, ruthenium, iridium, osmium, platinum and palladium. Thehydrogenation catalyst may include a refractory oxide or a silicate as abinder.

Hydrogenation reaction conditions and catalysts are described inEuropean Patent No. 0 583 836 to Eilers et al., entitled “Process ForThe Preparation of Hydrocarbon Fuels;” European Patent No. 0 668 342 toEilers et al., entitled “Lubricating Base Oil Preparation Process.”Hydrogenation reaction conditions and catalysts are also described inU.S. Pat. No. 5,371,308 to Gosselink et al., entitled “Process For ThePreparation Of Lower Olefins;” which is incorporated by referenceherein.

At least a portion of the second hydrocarbon stream may enterdehydrogenation-isomerization unit 110 via second conduit 714. At leasta portion of the paraffins in the second hydrocarbon stream may bedehydrogenated to olefins. At least a portion of the resulting olefinsand at least a portion of the olefins that were already present in thefeed stream may be isomerized to produce a second hydrocarbon stream.Process conditions used in dehydrogenation-isomerization unit 110 may bethe same as previously described for Systems 100, 200 and 300. At leasta portion of the resulting olefinic hydrocarbon stream and at least aportion of the unreacted hydrocarbons in the second hydrocarbon streammay form a third hydrocarbon stream.

In an embodiment, olefins may be separated, if desired, from the thirdhydrocarbon stream through techniques generally known in the art (e.g.,distillation, molecular sieves, extraction, adsorption,adsorption/desorption, and/or membranes). Separation of at least aportion of the branched olefins from the linear olefins and paraffinsmay increase the concentration of branched olefins entering thehydroformylation unit. In addition, separation of at least a portion ofthe branched olefins from the linear olefins and paraffins may influencethe ratio of linear to branched olefins produced in the hydroformylationunit.

Referring to FIG. 14, a third hydrocarbon stream may exitdehydrogenation-isomerization unit 110 and enter separation unit 118 viaseparation conduit 120. Separation unit 118 may produce at least twostreams, a branched olefins stream and a linear olefins and paraffinsstream. In separation unit 118, separation of branched olefins fromlinear olefins and paraffins may be performed using techniques describedearlier for system 100.

At least a portion of the linear olefins and paraffins stream may berecycled transported to other processing units and/or stored on site. Inan embodiment, at least a portion of the linear olefins and paraffinsstream may be combined with first hydrocarbon stream in first conduit712 via linear olefins and paraffins recycle conduit 122. The combinedstream may enter hydrogenation unit 710 via first conduit 712 tocontinue the process to produce aliphatic alcohols. In some embodiments,the linear olefins and paraffins stream may be introduced directly intohydrogenation unit 710. In other embodiments, at least a portion of thelinear olefins and paraffins stream may be combined with the secondhydrocarbon stream upstream of the dehydrogenation-isomerization unit.The combined stream may enter the dehydrogenation-isomerization unit tocontinue the process to produce aliphatic alcohols. In some embodiments,a linear olefins and paraffins stream may be introduced directly intothe dehydrogenation-isomerization unit.

At least a portion of the branched olefins stream may be transported andutilized in other processing streams and/or stored on site via branchedolefins conduit 124. In some embodiments, at least a portion of abranched olefins stream may exit separation unit 118 and be introducedinto third conduit 716 via branched olefins conduit 124. In otherembodiments, at least a portion of a branched olefins stream may exitseparation unit 118 and be introduced directly into a hydroformylationunit.

The third hydrocarbon stream may exit dehydrogenation-isomerization unit110 and be introduced into hydroformylation unit 116 via third conduit716. The third hydrocarbon stream may include branched olefins. Anaverage carbon number of hydrocarbons in the third hydrocarbon streammay range from 7 to 18. In certain embodiments, hydrocarbons in a thirdhydrocarbon stream may have an average carbon number from 10 to 17. Insome embodiments, hydrocarbons in the third hydrocarbon stream may havean average carbon number from 10 to 13. In other embodiments, an averagecarbon number of the hydrocarbons in a feed stream may range from 14 to17. At least a portion of the olefins in the third hydrocarbon streammay be hydroformylated to produce aliphatic alcohols using processconditions as previously described for System 100.

In certain embodiments, it may be desirable to adjust the olefin andparaffin concentration entering hydroformylation unit 116 depending onthe source of the olefin stream as previously described for System 100.An olefinic stream may be added to a process stream that contains lessthan 50 percent mono-olefins upstream of a hydroformylation unit toproduce a process stream that is greater than 50 percent mono-olefins.In some embodiments, a process stream containing about 80 percent linearolefins and 20 percent paraffins may be added to a process streamcontaining primarily branched olefins upstream of a hydroformylationunit. Hydroformylation of olefins with the combined stream may result ina mixed stream containing branched and linear aliphatic alcohols.

In an embodiment, a fourth hydrocarbon stream may be added to a processstream upstream of the hydroformylation unit. The fourth hydrocarbonstream may have an olefin content that ranges between about 1 percentand about 99 percent relative to the total hydrocarbon content. In otherembodiments, an olefin content of a fourth hydrocarbon stream may begreater than 80 percent relative to the total hydrocarbon content.

The hydroformylation reaction mixture stream may enter separator 126 viafourth conduit 718. Separation of at least a portion of paraffins and atleast a portion of olefins from the hydroformylation reaction mixturemay be accomplished as previously described for System 100. In separator126 at least two streams, a bottom stream and a top stream, may beproduced. The bottom stream may be recycled back to hydroformylationunit 116 via recycle conduit 130. The top stream may be purified andseparated to produce at least two streams, a paraffins and unreactedolefins stream and a crude aliphatic alcohol product stream. Methodsused for purification and separation, in certain embodiments, may be thesame as those described for System 100. The crude aliphatic alcoholproduct stream may be further purified to form an aliphatic alcoholproduct stream. The aliphatic alcohol product stream may includebranched aliphatic alcohols (e.g., branched primary alcohols). Thealiphatic alcohol product stream may exit separator 126 via productconduit 132 to be stored on site, sold commercially, transportedoff-site, and/or utilized in other processing units (e.g.,oxyalkylation, sulfation unit).

At least a portion of a paraffins and unreacted olefins stream may becombined with the second hydrocarbon stream in second conduit 714upstream of dehydrogenation-isomerization unit 110 to produce a combinedstream. The combined stream may be introduced intodehydrogenation-isomerization unit 110 and at least a portion of theparaffins in the combined stream may be dehydrogenated to olefins. Theresulting olefins may be isomerized to branched olefins. In anembodiment, a paraffins and unreacted olefins stream may be introduceddirectly into dehydrogenation-isomerization unit 110.

In certain embodiments, at least a portion of a paraffins and unreactedolefins stream may be combined upstream of the hydrogenation unit toproduce a combined stream. The combined stream may be introduced intothe hydrogenation unit. At least a portion of the olefins and at least aportion of by-products from the hydroformylation reaction may behydrogenated to paraffins. The resulting paraffins may be dehydrogenatedand isomerized in the dehydrogenation-isomerization unit. In anembodiment, a paraffins and unreacted olefins stream may be introduceddirectly into the hydrogenation unit.

In certain embodiments, a first hydrocarbon stream may contain unwantedcompounds (e.g., oxygenates and dienes) that may reduce catalystselectivity in a dimerization process used to produce aliphaticalcohols. Removal of the unwanted compounds may be performed byhydrogenation of the first hydrocarbon stream. Hydrogenation of thefirst hydrocarbon stream, in certain embodiments, may produce ahydrocarbon stream that includes greater than 90 percent paraffins. Thehydrogenated hydrocarbon stream may be dehydrogenated to produce anolefinic stream. The catalyst used in the dehydrogenation process maycontrol the position of the olefin double bond. In certain embodiments,an olefinic hydrocarbon stream may include olefins in which greater than70 percent of the olefins are alpha-olefins of a linear carbon skeletalstructure. In other embodiments, an olefinic hydrocarbon stream mayinclude olefins in which 50 percent or more of the olefin moleculespresent may be internal olefins.

Referring to System 800 as depicted in FIG. 15, a first hydrocarbonstream may be introduced into hydrogenation unit 710 via first conduit712. The first hydrocarbon stream includes olefins and paraffins.Hydrocarbons in the first hydrocarbon stream may have an average carbonnumber from 4 to 9. In certain embodiments, hydrocarbons in a firsthydrocarbon stream may have an average carbon number from 5 to 8. Insome embodiments, hydrocarbons in a first hydrocarbon stream may have anaverage carbon number from 5 to 7. In other embodiments, hydrocarbons ina first hydrocarbon stream may have an average carbon number from 5 to9. In hydrogenation unit 710, at least a portion of the olefins in thefirst hydrocarbon stream may be hydrogenated to paraffins to produce asecond hydrocarbon stream. Reaction conditions in the hydrogenation unit710, may be the same as previously described for System 700.

At least a portion of the second hydrocarbon stream may exithydrogenation unit 710 and enter dehydrogenation unit 618 via secondconduit 810. At least a portion of the unreacted paraffins in the secondhydrocarbon stream may be dehydrogenated to produce an olefinichydrocarbon stream by use of a catalyst selected from a wide range ofcatalyst types. For example, the catalyst may be based on a metal ormetal compound deposited on a porous support. The metal or metalcompound may be selected from, but is not limited to, chrome oxide, ironoxide and noble metals. Techniques of preparing catalysts, forperforming the dehydrogenation step and for performing associatedseparation steps may be the same as described for Systems 500 and 600.

Reaction conditions in dehydrogenation unit 618 may be varied to controlunwanted side products (e.g., coke, dienes, oligomers, cyclizedhydrocarbons) and control double bond position in the olefin. In certainembodiments, temperatures may range from greater than 300° C. to lessthan 700° C. In other embodiments, a reaction temperature may range fromabout 450° C. to about 550° C. During the dehydrogenation reaction, thepressures in dehydrogenation unit 618 may range from greater 0.010atmosphere (1 kPa) to about 25.0 atmospheres (2534 kPa). In anembodiment, a total pressure of dehydrogenation unit 618 during thereaction may range from about 0.010 atmosphere (1 kPa) to about 15.0atmospheres (15200 kPa). In certain embodiments, pressure indehydrogenation unit 618 may range from about 1.0 atmosphere (101 kPa)to about 5.0 atmospheres (510 kPa). In some embodiments, hydrogen may befed into dehydrogenation unit 618 together with the paraffins andunreacted olefins stream in order to prevent coke from forming. Thehydrogen to paraffins molar ratio may be set between about 0.1 moles ofhydrogen to about 20 moles of paraffins. In some embodiments, hydrogento paraffin molar ratio is about 1 to 10.

The amount of time (e.g., the residence time) that a process streamremains in dehydrogenation unit 618 may determine, to some extent, theamount of olefins produced. Generally, the longer a process streamremains in dehydrogenation unit 618, the conversion level of paraffinsto olefins increases until an olefin-paraffin thermodynamic equilibriumis obtained. The residence time of the paraffins and unreacted olefinsstream in dehydrogenation unit 618 may be selected such that theconversion level of paraffins to olefins may be kept below 50 molepercent. In certain embodiments, a conversion level of paraffins toolefins may be kept in the range from 5 to 30 mole percent. By keepingthe conversion level low, side reactions may be prevented (e.g., dieneformation and cyclization reactions).

In certain embodiments, at least a portion of non-converted paraffinsmay be separated from a third hydrocarbon stream using generally knowntechniques. Such separation may be accomplished by extraction,distillation or adsorption techniques. The paraffins may be recycled todehydrogenation unit 618 to undergo dehydrogenation to continue theprocess to produce aliphatic alcohols.

At least a portion of the third hydrocarbon steam may exit thedehydrogenation unit 618 and enter dimerization unit 410 via thirdconduit 812. In dimerization unit 410, at least a portion of the olefinsin the third hydrocarbon stream may be dimerized. The conditions of theolefin dimerization may be controlled, as previously described forSystem 400. The resulting dimerized olefins and the unreactedhydrocarbons in the third hydrocarbon stream may exit dimerization unit410 as a fourth hydrocarbon stream.

In an embodiment, depicted in FIG. 16, a separation unit may be used toseparate the produced dimerized olefins from the unreacted hydrocarbonsin the fourth hydrocarbon stream. In an embodiment, at least a portionof fourth hydrocarbon stream may exit dimerization unit 410 and enterseparation unit 416 via conduit 418. In separation unit 416 the reactionmixture may be separated into a produced dimerized olefins stream and aparaffins and unreacted olefins stream (e.g., by fractionaldistillation). The produced dimerized olefins stream may exit separationunit 416 and be introduced into fourth conduit 814 via conduit 422. Theparaffins and unreacted olefins stream may contain hydrocarbons with acarbon number less than 8. At least a portion of the paraffins andunreacted olefins stream may be recycled into dehydrogenation unit 618via conduit 420. In other embodiments, a paraffins and unreacted olefinsstream may be combined with a process stream upstream of thedehydrogenation unit. In certain embodiments, a paraffins and unreactedolefins stream may be combined with a process stream upstream of thehydrogenation unit. In some embodiments, a paraffins and unreactedolefins stream may be recycled directly into the hydrogenation unit.

At least a portion of the fourth hydrocarbon stream may exitdimerization unit 410 and be introduced into hydroformylation unit 116via fourth conduit 814. The fourth hydrocarbon stream includes branchedolefins. At least a portion of the olefins in the fourth hydrocarbonstream may be hydroformylated to produce aliphatic alcohols usingprocess conditions as previously described for System 100.

In certain embodiments, it may be desirable to adjust the olefin andparaffin concentration in hydroformylation unit 116 depending on thesource of the olefin stream as previously described for System 100. Anolefinic stream may be added to a process stream that contains less than50 percent mono-olefins upstream of a hydroformylation unit to produce aprocess stream that is greater than 50 percent mono-olefins. In someembodiments, a fifth hydrocarbon stream containing about 80 percentlinear olefins and 20 percent paraffins may be added to a process streamcontaining primarily branched olefins upstream of a hydroformylationunit. Hydroformylation of olefins in the combined stream may result in amixed stream containing branched and linear aliphatic alcohols.

In an embodiment, a fifth hydrocarbon stream may be added to a processstream upstream of the hydroformylation unit. The olefin content of thefifth hydrocarbon stream may range between about 1 percent and about 99percent relative to the total hydrocarbon content. In certainembodiments, an olefin content of a fifth hydrocarbon stream may begreater than 80 percent relative to the total hydrocarbon content.

The hydroformylation reaction mixture stream may enter separator 126 viafifth conduit 816. Separation of at least a portion the crude aliphaticalcohols from the hydroformylation reaction mixture may be accomplishedas previously described for System 100. In separator 126, at least twostreams, a bottom stream and a top stream, may be produced. The bottomstream may be recycled back to hydroformylation unit 116 via recycleconduit 130. The top stream may be purified and separated to produce atleast two streams, a paraffins and unreacted olefins stream and a crudealiphatic alcohol product stream. Methods used for purification andseparation, in certain embodiments, may be the same as those describedfor System 100. The crude aliphatic alcohol product stream may befurther purified to form an aliphatic alcohol product stream. Thealiphatic alcohol product stream may include branched aliphatic alcohols(e.g., branched primary alcohols). The aliphatic alcohol product streammay exit separator 126 via product conduit 132 to be stored on site,sold commercially, transported off-site, and/or utilized in otherprocessing units (e.g., oxyalkylation unit and sulfation unit).

At least a portion of a paraffins and unreacted olefins stream may exitseparator 126 and be recycled, combined with other process streams, sentto other processing units and/or be stored on site via sixth conduit818. In certain embodiments, a paraffins and unreacted olefins streammay be further separated into a hydrocarbons stream including paraffinsand unreacted olefins with a carbon number less than 8. The hydrocarbonstream including paraffins and unreacted olefins with a carbon numberless than 8 may be introduced upstream of and/or into dehydrogenationunit 618. In other embodiments, a hydrocarbon stream including paraffinsand unreacted olefins with a carbon number less than 8 may be introducedupstream of and/or into the hydrogenation unit.

In certain embodiments, a hydrocarbon stream from a dimerization unitmay be combined with a hydrocarbon stream from an isomerization unit toproduce a combined stream. The combined stream may be introduced into ahydroformylation unit. Combining streams from the two units may resultin a more economically valuable process to produce branched aliphaticalcohols. Referring to System 900, as depicted in FIG. 17, a firsthydrocarbon stream may be introduced into hydrogenation unit 710 viafirst conduit 712. The first hydrocarbon stream includes olefins andparaffins. In hydrogenation unit 710, at least a portion of the olefinsin the first hydrocarbon stream may be hydrogenated to paraffins toproduce a second hydrocarbon stream. Reaction conditions in thehydrogenation unit 710, may be the same as previously described forSystem 700.

At least a portion of the second hydrocarbon stream may enterdehydrogenation unit 618 via second conduit 810. At least a portion ofthe paraffins in the second hydrocarbon stream may be dehydrogenatedusing process conditions as previously described for Systems 300, 500,600 and/or 800. At least a portion of the resulting olefinic hydrocarbonstream and at least a portion of the unreacted hydrocarbons in thesecond hydrocarbon stream may form a third hydrocarbon stream.

At least a portion of the third hydrocarbon steam may exit thedehydrogenation unit and enter dimerization unit 410 via third conduit812. In dimerization unit 410, at least a portion of the olefins may bedimerized. At least a portion of the dimerized olefins exit dimerizationunit 410 as a fourth hydrocarbon stream. The conditions of the olefindimerization and isomerization may be controlled, as previouslydescribed for System 400.

At least a portion of the fourth hydrocarbon stream may exitdimerization unit 410 and enter hydroformylation unit 116 via fourthconduit 814. In certain embodiments, a fourth hydrocarbon stream mayinclude olefins with an average carbon number that ranges from 8 to 16.At least a portion of a sixth hydrocarbon stream may be introduced intofourth conduit 814 via sixth conduit 910 upstream of hydroformylationunit 116 to produce a combined stream. The sixth hydrocarbon stream maybe a stream exiting from isomerization unit 514. Isomerization unit 514may be fed by a fifth hydrocarbon stream containing olefins andparaffins via a fifth conduit 912. In isomerization unit 514, at least aportion of the olefins in the fifth hydrocarbon stream may be isomerizedto branched olefins to produce the sixth hydrocarbon stream usingprocess conditions previously described for Systems 500 and 600. Thesixth hydrocarbon stream may exit isomerization unit 514 via sixthconduit 910 and be combined with fourth hydrocarbon stream in conduit814.

The combined stream may enter hydroformylation unit 116 and at least aportion of the olefins in the combined stream may be hydroformylated toproduce aliphatic alcohols. In certain embodiments, a combinedhydrocarbon stream may include hydrocarbons with an average carbonnumber ranging from 7 to 18. Hydroformylation reaction conditions andsubsequent purification steps may be the same as previously describedfor System 100. The resulting alcohol products may be branched aliphaticalcohols with an average carbon number ranging from 8 to 19.

In certain embodiments, it may be desirable to adjust the olefin andparaffin concentration entering hydroformylation unit 116 and/orisomerization unit 514 depending on the source of the olefin stream aspreviously described for Systems 100, 500 and 600 in FIGS. 1, 9 and 12.A paraffinic stream containing less than 50 percent mono-olefins may beadded to a process stream upstream of an isomerization unit to produce aprocess stream that is less than 50 percent mono-olefins. In someembodiments, a seventh hydrocarbon stream containing about 80 percentlinear olefins and 20 percent paraffins may be added to a process streamcontaining primarily branched olefins upstream of a hydroformylationunit and/or isomerization unit. Subsequent hydroformylation of theolefins in the combined stream may result in a mixed stream containingbranched and linear aliphatic alcohols. A paraffinic stream may beintroduced upstream of isomerization unit via seventh conduit 914.

In an embodiment, a seventh hydrocarbon stream may be added to processstream upstream of the hydroformylation unit. The olefin content of aseventh hydrocarbon stream may range between about 1 percent and about99 percent relative to the total hydrocarbon content. A paraffinicstream containing greater than 50 percent mono-olefins may be added to aprocess stream upstream of a hydroformylation unit to produce a processstream that is greater than 50 percent mono-olefins. In certainembodiments, an olefin content of a seventh hydrocarbon stream may begreater than 80 percent relative to the total hydrocarbon content.

The hydroformylation reaction mixture stream may enter separator 126 viaeighth conduit 916. Separation of at least a portion of crude aliphaticalcohols from the hydroformylation reaction mixture may be accomplishedas previously described for System 100. In separator 126 at least twostreams, a bottom stream and a top stream, may be produced. The bottomstream may be recycled back to hydroformylation unit 116 via recycleconduit 130. The top stream may be purified and separated to produce atleast two streams, a paraffins and unreacted olefins stream and a crudealiphatic alcohol product stream. Methods used for purification andseparation, in certain embodiments, may be the same as those describedfor System 100. The crude aliphatic alcohol product stream may befurther purified to form an aliphatic alcohol product stream. Thealiphatic alcohol product stream may include branched aliphatic alcohols(e.g., branched primary alcohols). The aliphatic alcohol product streammay exit separator 126 via product conduit 132 to be stored on site,sold commercially, transported off-site, and/or utilized in otherprocessing units (e.g., an oxyalkylation and/or a sulfation unit).

In certain embodiments, a paraffins and unreacted olefins stream may beintroduced upstream of and/or into dehydrogenation unit 618 and/orhydrogenation unit 710 via other ports and/or conduits via ninth conduit918. In other embodiments, a paraffins and unreacted olefins stream maybe further separated into a hydrocarbons stream including paraffins andunreacted olefins with a carbon number less than 9. At least a portionof the paraffins and unreacted olefins stream may be introduced upstreamof the dehydrogenation unit and/or the hydrogenation unit via otherports and/or conduits.

In certain embodiments, a first hydrocarbon stream may contain unwantedcompounds (e.g., oxygenates and dienes) that may reduce catalystselectivity in an isomerization process used to produce aliphaticalcohols. Removal of the unwanted compounds may be performed byhydrogenation of the first hydrocarbon stream. Hydrogenation of thefirst hydrocarbon stream, in certain embodiments, may produce ahydrocarbon stream that includes greater than 90 percent paraffins. Thehydrogenated hydrocarbon stream may be dehydrogenated to produce anolefinic stream. The catalyst used in the dehydrogenation process maycontrol the position of the olefin double bond. In certain embodiments,an olefinic hydrocarbon stream may include olefins in which greater than70 percent of the olefins are alpha-olefins of a linear carbon skeletalstructure. In other embodiments, an olefinic hydrocarbon stream mayinclude olefins in which 50 percent or more of the olefin moleculespresent may be internal olefins.

Referring to System 1000 as depicted in FIG. 18, a first hydrocarbonstream may be introduced into hydrogenation unit 710 via first conduit712. The first hydrocarbon stream includes olefins and paraffins. Afirst hydrocarbon stream may include hydrocarbons with an average carbonnumber from 7 to 18. In certain embodiments, a first hydrocarbon streammay include hydrocarbons with an average carbon number from 10 to 17. Insome embodiments, a first hydrocarbon stream may include hydrocarbonswith an average carbon number from 10 to 13. In other embodiments, afirst hydrocarbon stream may include hydrocarbons with an average carbonnumber from 14 to 17. In hydrogenation unit 710, at least a portion ofthe olefins in the first hydrocarbon stream may be hydrogenated toparaffins to produce a second hydrocarbon stream. Reaction conditions inthe hydrogenation unit 710, may be the same as previously described forSystem 700.

At least a portion of the second hydrocarbon stream may exithydrogenation unit 710 and enter dehydrogenation unit 618 via secondconduit 810. At least a portion of the paraffins in the secondhydrocarbon stream may be dehydrogenated using process conditions aspreviously described for System 600.

At least a portion of the third hydrocarbon steam may exit thedehydrogenation unit 618 and enter isomerization unit 514 via thirdconduit 812. Conditions of the olefin isomerization may be controlled,as previously described in Systems 500 and 600, such that the number ofcarbon atoms in the olefin before and after isomerization issubstantially the same. At least a portion of the olefins in thecombined stream may be isomerized to branched olefins in isomerizationunit 514 to produce a fourth hydrocarbon stream.

The fourth hydrocarbon stream may exit isomerization unit 514 and beintroduced into hydroformylation unit 116 via fourth conduit 1010. Thefourth hydrocarbon stream includes branched olefins. An average carbonnumber of hydrocarbons in the fourth hydrocarbon stream may range from 7to 18. In certain embodiments, an average carbon number of hydrocarbonsin the fourth hydrocarbon stream may range from 10 to 17. In someembodiments, an average carbon number of hydrocarbons in the fourthhydrocarbon stream may range from 10 to 13. In other embodiments, anaverage number of hydrocarbons in the fourth hydrocarbon stream mayrange from 14 to 17. At least a portion of the olefins may behydroformylated using process conditions as previously described forSystem 600.

In certain embodiments, it may be desirable to adjust the olefin andparaffin concentration entering isomerization unit 514 and/orhydroformylation unit 116 depending on the source of the olefin streamas previously described for System 600. An olefinic stream may be addedto a process stream that contains less than 50 percent mono-olefinsupstream of an isomerization unit to produce a process stream that isless than 50 percent mono-olefins. In some embodiments, a fifthhydrocarbon stream containing about 20 percent linear olefins and 80percent paraffins may be added to a process stream containing primarilybranched olefins upstream of a hydroformylation unit. Subsequenthydroformylation of the olefins in the combined stream may result in amixed stream containing branched and linear aliphatic alcohols.

In an embodiment, a fifth hydrocarbon stream may be added to processstream upstream of the hydroformylation unit and/or isomerization unitthat contains an olefin content of between about 1 percent and about 99percent relative to the total hydrocarbon content. An olefinic streammay be added to a process stream that contains greater than 50 percentmono-olefins upstream of a hydroformylation unit to produce a processstream that is greater than 50 percent mono-olefins. In otherembodiments, an olefin content of a fifth hydrocarbon stream may begreater than 80 percent relative to the total hydrocarbon content.

In an embodiment, olefins may be separated, if desired, from the fourthhydrocarbon stream through techniques generally known in the art (e.g.,distillation, molecular sieves, extraction, adsorption,adsorption/desorption and/or membranes). Separation of at least aportion of the branched olefins from the linear olefins and paraffinsmay increase the concentration of branched olefins entering thehydroformylation unit. In addition, separation of at least a portion ofthe branched olefins from the linear olefins and paraffins may influencethe ratio of linear to branched olefins produced in the hydroformylationunit.

Referring to FIG. 19, a fourth hydrocarbon stream may exit isomerizationunit 514 and enter separation unit 118 via separation conduit 614.Separation unit 118 may produce at least two streams, a branched olefinsstream and a linear olefins and paraffins stream. In separation unit118, separation of branched olefins from linear olefins and paraffinsusing techniques described for System 100.

At least a portion of the linear olefins and paraffins stream may berecycled, transported to other processing units and/or stored on site.In an embodiment, at least a portion of the linear olefins and paraffinsstream may be combined with first hydrocarbon stream in first conduit712 via linear olefins and paraffins recycle conduit 616. The combinedstream may enter hydrogenation unit 710 via first conduit 712 tocontinue the process to produce aliphatic alcohols. In some embodiments,the linear olefins and paraffins stream may be introduced directly intothe hydrogenation unit. In other embodiments, at least a portion of thelinear olefins and paraffins stream may be combined with the secondhydrocarbon stream upstream of the dehydrogenation unit. The combinedstream may enter the dehydrogenation unit to continue the process toproduce aliphatic alcohols. In some embodiments, a linear olefins andparaffins stream may be introduced directly into the dehydrogenationunit.

At least a portion of the branched olefins stream may be transported andutilized in other processing streams and/or stored on site via branchedolefins conduit 620. In some embodiments, at least a portion of abranched olefins stream may exit separation unit 118 and be combinedwith third hydrocarbon stream in fourth conduit 1010 upstream ofhydroformylation unit 116 via branched olefins conduit 620. In otherembodiments, at least a portion of a branched olefins stream may exitseparation unit 118 and be introduced directly into the hydroformylationunit.

Referring to FIG. 18, the hydroformylation reaction mixture stream mayenter separator 126 via fifth conduit 1012. Separation of at least aportion the crude aliphatic alcohols from the hydroformylation reactionmixture may be accomplished as previously described for System 100. Inseparator 126 at least two streams, a bottom stream and a top stream,may be produced. The bottom stream may be recycled back tohydroformylation unit 116 via recycle conduit 130. The top stream may bepurified and separated to produce at least two streams, a paraffins andunreacted olefins stream and a crude aliphatic alcohol product stream.Methods used for purification and separation, in certain embodiments,may be the same as those described for System 100. The crude aliphaticalcohol product stream may be further purified to form an aliphaticalcohol product stream. The aliphatic alcohol product stream may includebranched aliphatic alcohols (e.g., branched primary alcohols). Thealiphatic alcohol product stream may exit separator 126 via productconduit 132 to be stored on site, sold commercially, transportedoff-site, and/or utilized in other processing units (e.g., anoxyalkylation and a sulfation unit).

At least a portion of a paraffins and unreacted olefins stream may exitseparator 126 and be recycled, combined with other process streams, sentto other processing units and/or be stored on site via sixth conduit1014. At least a portion of the paraffins and unreacted olefins streammay be combined with the second hydrocarbon stream in second conduit 810upstream of dehydrogenation unit 618 via sixth conduit 1014 to produce acombined stream. The combined stream may be introduced intodehydrogenation unit 618 and at least a portion of the paraffins in thecombined stream may be dehydrogenated to olefins. In an embodiment, aparaffins and unreacted olefins stream may be introduced directly intodehydrogenation unit 618. The concentration of the olefins in theolefinic hydrocarbon stream may be between 5 and 50 percent by weight.In certain embodiments, a concentration of the olefins may range between10 and 20 percent by weight. Hydrocarbons in a paraffins and unreactedolefins stream may have an average carbon number from 10 to 18. Anaverage carbon number of the hydrocarbons in a paraffins and unreactedolefins stream may range, in certain embodiments, from 10 to 17. In someembodiments, hydrocarbons in a paraffins and unreacted olefins streammay range from 10 to 13. In other embodiments, an average carbon numberof the hydrocarbons in a paraffins an unreacted olefins stream may rangefrom 14 to 17. In some embodiments, a paraffins and unreacted olefinsstream may be introduced directly into and/or upstream of thehydrogenation unit.

Aliphatic alcohols may be converted to oxy alcohols, sulfates or othercommercial products. At least a portion of the aliphatic alcohols in thealcohol product stream may be reacted in an oxyalkylation unit with anepoxide (e.g., ethylene oxide, propylene oxide, butylene oxide) in thepresence of a base to produce an oxyalkyl alcohol. Condensation of analcohol with an epoxide allows the alcohol functionality to be expandedby one or more oxy groups. The number of oxy groups may range from 3 to12. For example, reaction of an alcohol with ethylene oxide may producealcohol products having between 3 to 12 ethoxy groups. Reaction of analcohol with ethylene oxide and propylene oxide may produce alcoholswith an ethoxy/propoxy ratio of ethoxy to propoxy groups from about 4:1to about 12:1. In some embodiments, a substantial proportion of alcoholmoieties may become combined with more than three ethylene oxidemoieties. In other embodiments, an approximately equal proportion may becombined with less than three ethylene oxide moieties. In a typicaloxyalkylation product mixture, a minor proportion of unreacted alcoholmay be present in the product mixture. In an embodiment, at least aportion of the aliphatic alcohol product stream may be formed bycondensing a C₅ to C₃₁, aliphatic alcohol with an epoxide. In certainembodiments, a C₅ to C₁₅ branched primary alcohol may be condensed withethylene oxide and/or propylene oxide. In other embodiments, a C₁₁ toC₁₋₇ branched primary alcohol may be condensed with ethylene oxideand/or propylene oxide. The resulting oxyalkyl alcohols may be soldcommercially, transported off-site, stored on site and/or used in otherprocessing units. In some embodiments, an oxyalkyl alcohol may besulfated to form an anionic surfactant.

In an embodiment, at least a portion of the alcohols in the aliphaticalcohol product stream may be added to a base. The base may be an alkalimetal or alkaline earth metal hydroxide (e.g., sodium hydroxide orpotassium hydroxide). The base may act as a catalyst for theoxyalkylation reaction. An amount from about 0.1 percent by weight toabout 0.6 percent by weight of a base, based on the total weight ofalcohol, may be used for oxyalkylation of an alcohol. In an embodiment,a weight percent of a base may range from about 0.1 percent by weight to0.4 percent by weight based on the total alcohol amount. The reaction ofthe alcohol with the base may result in formation of an alkoxide. Theresulting alkoxide may be dried to remove any water present. The driedalkoxide may be reacted with an epoxide. An amount of epoxide used maybe from about 1 mole to about 12 moles of epoxide per mole of alkoxide.A resulting alkoxide-epoxide mixture may be allowed to react until theepoxide is consumed. A decrease in overall reaction pressure mayindicate that the reaction is complete.

Reaction temperatures in an oxyalkylation unit may range from about 120°C. to about 220° C. In an embodiment, reaction temperatures may rangefrom about 140° C. to about 160° C. Reaction pressures may be achievedby introducing to the reaction vessel the required amount of epoxide.Epoxides have a high vapor pressure at the desired reaction temperature.For consideration of process safety, the partial pressure of the epoxidereactant may be limited, for example, to less than 4 atmospheres (413kPa). Other safety measures may include diluting the reactant with aninert gas such as nitrogen. For example, inert gas dilution may resultin a vapor phase concentration of reactant of about 50 percent or less.In some embodiments, an alcohol-epoxide reaction may be safelyaccomplished at a greater epoxide concentration, a greater totalpressure and a greater partial pressure of epoxide if suitable,generally known, safety precautions are taken to manage the risks ofexplosion. With respect to ethylene oxide, a total pressure from about 3atmospheres (304 kPa) to about 7 atmospheres (709 kPa) may be used.Total pressures of ethylene oxide from about 1 atmosphere (101 kPa) toabout 4 atmospheres (415 kPa) may be used in certain embodiments. In anembodiment, total pressures from about 1.5 atmospheres (150 kPa) toabout 3 atmospheres (304 kPa) with respect to ethylene oxide may beused. The pressure may serve as a measure of the degree of the reaction.The reaction may be considered substantially complete when the pressureno longer decreases with time.

Aliphatic alcohols and oxyalkyl alcohols may be derivatized to formcompositions (e.g., sulfonates, sulfates, phosphates) useful incommercial product formulations (e.g., detergents, surfactants, oiladditives, lubricating oil formulations). For example, alcohols may besulfurized with SO₃ to produce sulfates. The term “sulfurized” refers toa sulfur atom or sulfur containing functionality being added to a carbonor oxygen. Sulfurization processes are described in U.S. Pat. No.6,462,215 to Jacobson et al., entitled “Sulfonation, Sulfation andSulfamation”; U.S. Pat. No. 6,448,435 to Jacobson et al., entitled“Sulfonation, Sulfation and Sulfamation”; U.S. Pat. No. 3,462,525 toLevinsky et al, entitled, “Dental Compositions Comprising Long-ChainOlefin Sulfonates;” U.S. Pat. No. 3,428,654 to Rubinfeld et al.,entitled, “Alkene Sulfonation Process and Products;” U.S. Pat. No.3,420,875 to DiSalvo et al., entitled, “Olefin Sulfonates;” U.S. Pat.No. 3,506,580 to Rubinfeld et al., entitled, “Heat-Treatment OfSulfonated Olefin Products;” and U.S. Pat. No. 3,579,537 to Rubinfeld,entitled, “Process For Separation Of Sultones From Alkenyl SulfonicAcids,” all of which are incorporated herein by reference.

A general class of aliphatic alcohol sulfates may be characterized bythe chemical formula: (R—O-(A)_(x)-SO₃)_(n)M. R′ represents thealiphatic moiety. “A” represents a moiety of an alkylene oxide; xrepresents the average number of A moieties per R—O moiety and may rangefrom 0 to 15; and n is a number depending on the valence of cation M.Examples of cation M include, but are not limited to, alkali metal ions,alkaline earth metal ions, ammonium ions and/or mixtures thereof.Examples of cations include, but are not limited to, magnesium,potassium, monoethanol amine, diethanol amine or triethanol amine.

Aliphatic and oxyalkyl alcohols may be sulfated in a sulfation unit.Sulfation procedures may include the reaction of sulfur trioxide (SO₃),chlorosulfonic acid (ClSO₃H), sulfamic acid (NH₂SO₃H) or sulfuric acidwith an alcohol. In an embodiment, sulfur trioxide in concentrated(e.g., fuming) sulfuric acid may be used to sulfate alcohols. Theconcentrated sulfuric acid may have a concentration of about 75 percentby weight to about 100 percent by weight in water. In an embodiment,concentrated sulfuric acid may have a concentration of about 85 percentby weight to about 98 percent by weight in water. The amount of sulfurtrioxide may range from about 0.3 mole to about 1.3 moles of sulfurtrioxide per mole of alcohol. In certain embodiments, an amount ofsulfur trioxide may range from about 0.4 moles to about 1.0 moles ofsulfur trioxide per mole of alcohol.

In an embodiment, a sulfur trioxide sulfation procedure may includecontacting a liquid alcohol or an oxyalkyl alcohol and gaseous sulfurtrioxide in a falling film sulfator to produce a sulfuric acid ester ofthe alcohol. The reaction zone of the falling film sulfator may beoperated at about atmospheric pressure and at a temperature in the rangefrom about 25° C. to about 70° C. The sulfuric acid ester of the alcoholmay exit the falling film sulfator and enter a neutralization reactor.The sulfuric acid ester may be neutralized with an alkali metal solutionto form the alkyl sulfate salt or the oxyalkyl sulfate salt. Examples ofan alkali metal solution may include solutions of sodium or potassiumhydroxide.

The derivatized alcohols may be used in a wide variety of applications.An example of an application includes detergent formulations. Detergentformulations include, but are not limited to, granular laundry detergentformulation, liquid laundry detergent formulations, liquid dishwashingdetergent formulations and miscellaneous formulations. Examples ofmiscellaneous formulations may include general purpose cleaning agents,liquid soaps, shampoos and liquid scouring agents.

Granular laundry detergent formulations may include a number ofcomponents besides the derivatized alcohols (e.g., surfactants,builders, co-builders, bleaching agents, bleaching agent activators,foam controlling agents, enzymes, anti-graying agents, opticalbrighteners and stabilizers). Examples of other surfactants may includeionic, nonionic, amphoteric or cationic surfactants.

Liquid laundry detergent formulations may include the same components asgranular laundry detergent formulations. In certain embodiments, liquidlaundry detergent formulations may include less of an inorganic buildercomponent than granular laundry detergent formulations. Hydrotropes maybe present in the liquid detergent formulations. General purposecleaning agents may include other surfactants, builders, foam controlagents, hydrotropes and solubilizer alcohols.

The present formulations may include a large amount of the builder andco-builder components. In some embodiments, builder and co-buildercomponents may be about 90 percent by weight. To intensify the cleaningaction, the builder and co-builder components may, in other embodiments,be in amounts from about 5 percent to about 35 percent by weight, basedon the weight of the formulation. Examples of common inorganic buildersmay include phosphates, polyphosphates, alkali metal carbonates,silicates and sulfonates. Examples of organic builders may includepolycarboxylates, aminocarboxylates such asethylenediaminetetraacetates, nitrilotriacetates, hydroxycarboxylates,citrates, succinates, and substituted and unsubstituted alkane di- andpolycarboxylic acids. Another type of builder, useful in granularlaundry and built liquid laundry agents, includes various substantiallywater-insoluble materials, which are capable of reducing the waterhardness. An example of process to reduce water hardness is an ionexchange process. In an embodiment, complex sodium aluminosilicates,known as type A zeolites, may be useful for this purpose.

The present formulations may include percompounds with a bleachingaction. Examples of percompounds may include perborates, percarbonates,persulfonates and organic peroxy acids. Formulations containingpercompounds may also include stabilizing agents. Examples ofstabilizing agents may include magnesium silicate, sodiumethylenediaminetetraacetate or sodium salts of phosphonic acids. In someembodiments, bleach activators may be used to increase the efficiency ofthe inorganic persalts at lower washing temperatures. Substitutedcarboxylic acid amides, tetraacetylethylenediamine, substitutedcarboxylic acids may be useful for lower washing temperatures in otherembodiments. Examples of substitute carboxylic acids may includeisononyloxybenzenesulfonate and sodium cyanamide.

Examples of suitable hydrotropic substance include, but are not limitedto, alkali metal salts of benzene, toluene and xylenes, sulfonic acids;alkali metal salts of formic acid; citric and succinic acid; alkalimetal chlorides; urea; and mono-, di- and tri-ethanolamine. Examples ofsolubilizer alcohols may include ethanol, isopropanol, mono- orpoly-ethylene glycols, monopropylene glycol and ether alcohols.

Examples of foam control agents may include high molecular weight fattyacid soaps, paraffinic hydrocarbons and silicon containing defoamers. Inan embodiment, hydrophobic silica particles are efficient foam controlagents in laundry detergent formulations.

Examples of known enzymes that are effective in the laundry detergentformulations may include protease, amylase and lipase. Enzymes, whichhave an optimum performance at the design conditions of the washing andcleaning agent, may be used.

A large number of fluorescent whiteners are described in the literature.For the laundry washing formulations, the derivatives ofdiaminostilbene, disulfonates and substituted distyrybiphenyl may beused.

Water-soluble colloids of an organic nature may be used as anti-grayingagents. Examples of water-soluble anti-graying agents may includepolyanionic polymers such as polymers and copolymers of acrylic andmaleic acid, cellulose derivatives such as carboxymethyl cellulosemethyl- and hydroxethylcellulose.

The formulations may typically include one or more inert components. Forexample, the balance of liquid detergent formulations may typically bean inert solvent or diluent (e.g., water). Powdered or granulardetergent formulations typically contain quantities of inert filler orcarrier materials.

EXAMPLES Example 1 Isomerization of Olefins in a Fischer-Tropsch derivedHydrocarbon Stream

Carbon monoxide and hydrogen were reacted under Fischer-Tropsch processconditions to yield a hydrocarbon mixture of linear paraffins, linearolefins, a minor amount of dienes and a minor amount of oxygenates. TheFischer-Tropsch hydrocarbon stream was separated into differenthydrocarbon streams using fractional distillation techniques. Ahydrocarbon stream containing olefins and paraffins with an averagenumber of carbon atoms from 8 to 10 was obtained. The composition of theresulting C₈-C₁₀ hydrocarbon stream was analysed by gas chromatographyand is tabulated in Table 1. TABLE 1 Fischer-Tropsch Hydrocarbon StreamComposition Wt. % C₇ and lighter hydrocarbons 0.12 C₈ branched olefins0.02 C₈ linear olefins 0.75 1-Octene 0.69 n-Octane 2.21 C₉ branchedolefins 0.16 C₉ linear olefins 8.52 1-Nonene 8.07 n-Nonane 20.03 C₁₀branched olefins 0.28 C₁₀ linear olefins 22.92 1-Decene 20.87 n-Decane41.12 C₁₁ and heavier hydrocarbons 0.21 C₉-C₁₁ alcohols 3.56

A zeolite catalyst used for isomerization of linear olefins in thehydrocarbon stream was prepared in the following manner.Ammonium-ferrierite (645 grams) exhibiting a 5.4% loss on ignition andexhibiting the following properties: molar silica to alumina ratio of62:1, surface area of 369 square meters per gram (P/Po=0.03), sodacontent of 480 ppm and n-hexane sorption capacity of 7.3 g per 100 g ofammonium-ferrierite was loaded into a Lancaster mix muller. CATAPAL® Dalumina (91 grams) exhibiting a loss on ignition of 25.7% was added tothe muller. During a five-minute mulling period, 152 milliliters ofdeionized water was added to the alumina/ammonium-ferrierite mixture.Next, a mixture of 6.8 grams glacial acetic acid, 7.0 grams of citricacid and 152 milliliters of deionized water was slowly added to thealumina/ammonium-ferrierite mixture in the muller to peptize thealumina. The resulting alumina/ammonium-ferrierite/acid mixture wasmulled for 10 minutes. Over a period of 15 minutes, a mixture of 0.20grams of tetraamine palladium nitrate in 153 grams of deionized waterwas slowly added to mulled alumina/ammonium-ferrierite/acid mixture. Theresulting mixture exhibited a 90:10 ratio of zeolite to alumina and aloss on ignition of 43.5%. The zeolite/alumina mixture was shaped byextruding the mixture through a stainless steel die plate ( 1/16″ holes)of a 2.25 inch Bonnot extruder.

The moist zeolite/alumina extrudate was dried at 125° C. for 16 hours.After drying, the zeolite/alumina extrudate was longsbroken manually.The zeolite/alumina extrudate was calcined in flowing air at 200° C. fortwo hours. The temperature was raised to a maximum temperature of 500°C. and the zeolite/alumina extrudate was calcined for an additional twohours to yield an isomerization catalyst. The isomerization catalyst wasallowed to cool in a dessicator under a nitrogen atmosphere.

Stainless steel tubing, 1 inch OD, 0.6 inch ID and 26 inches long, wasused as an isomerization reactor. A thermowell extended 20 inches fromthe top of the stainless steel reactor tube. To load the reactor tube,the reactor tube was inverted and a piece of glass wool was transferreddown the wall of the reactor tube, over the thermowell and positioned atthe bottom of the reactor tube to serve as a plug for the reactor tube.Silicon carbide (20 mesh) was added to a depth of about 6 inches to thereactor tube. A second piece of glass wool was placed over the siliconcarbide. A mixture of 6.0 grams of the isomerization catalyst particles(6-20 mesh) and 45 grams of fresh silicon carbide (60-80 mesh) was addedto the reactor tube in two parts. The two-part addition distributed theisomerization catalyst evenly in the reactor tube and resulted in anisomerization catalyst bed of about 10 inches in length. A third pieceof glass wool was added to the top of the catalyst in the reactor tube.Silicon carbide (20 mesh) was layered onto the third piece of glasswool. A fourth piece of glass wool was positioned over the siliconcarbide to serve as a plug for the bottom of the reactor tube. Tomonitor the temperature of the reaction at various points in the reactortube, a multipoint thermocouple was inserted into the thermowell of thereactor tube. The temperature above, below and at three different placesin the catalyst bed was monitored. The reactor tube was inverted andinstalled in the furnace. The reactor tube was heated to the operatingtemperature of 280° C. over a four-hour period under flowing nitrogen.Once the temperature of 280° C. was obtained, the reactor tube was heldat the operating temperature for an additional two hours to conditionthe isomerization catalyst.

After conditioning the isomerization catalyst, the hydrocarbon streamwas pumped through the reactor tube at a flow rate of 60 g/hr. Nitrogen,at a flow rate of 6 L/hr, was passed over the isomerization catalystsimultaneously with the hydrocarbon stream. The hydrocarbon stream wasvaporized before contacting the isomerization catalyst. The reactor tubewas operated at an outlet pressure of 20 kPa above atmospheric pressure.

In Table 2, the weight percent of C₈-C₁₀ branched olefins, C₈-C₁₀ linearolefins and C₈-C₁₀ paraffins in the hydrocarbon stream at 0 hours and inthe reactor tube effluent after 24 and 48 hours of isomerization istabulated. Greater than 90% of the linear olefins in the hydrocarbonstream were converted into branched olefins in the isomerizationreactor. During the isomerization step, a small amount of materialboiling below C₈ was generated from cracking side reactions. Inaddition, a portion of the C₉-C₁₁ alcohols present in the feed wasdehydrated to yield additional olefins in the product. The averagenumber of alkyl branches on the C₈-C₁₀ olefins in the product was foundto be 1.0 as determined by ¹H NMR analysis. TABLE 2 Fischer-TropschHydrocarbon Stream Composition During 0 Hr 24 Hr 48 Hr IsomerizationReaction Wt. % Wt. % Wt. % C₈-C₁₀ branched olefins 0.46 33.04 33.16C₈-C₁₀ linear olefins 32.19 2.52 2.54 C₈-C₁₀ paraffins 63.19 63.32 63.27Branched to linear C₈ ₋₁₀ olefin ratio 0.1 13.1 13.1

Example 2 Isomerization of 1-Dodecene

1-dodecene was obtained from Shell Chemical Co. The composition of1-dodecene, as assayed by gas chromatography, is tabulated in Table 3.TABLE 3 1-Dodecene Composition Wt. % 1-Dodecene 98.0 Other C₁₀-C₁₄olefins 1.2 <C₁₀ hydrocarbons 0.2 >C₁₄ hydrocarbons 0.2 Paraffins 0.4Total C₁₀-C₁₄ hydrocarbons 99.6

1-dodecene was isomerized using the same reactor tube design andisomerization catalyst preparation as described in Example 1. A streamof 1-dodecene was pumped through a reactor tube at a flow rate of 90g/hr. Nitrogen, at a flow rate of 6 L/hr, was passed over theisomerization catalyst simultaneously with the stream of 1-dodecene. Thestream of 1-dodecene was vaporised before contacting the isomerizationcatalyst. The reactor tube was operated at an outlet pressure of 20 kPaabove atmospheric pressure and a temperature of 290° C.

Table 4 is a tabulation of the weight percent of less than C₁₀, C₁₀-C₁₄and greater than C₁₄ molecules in 1-dodecene at 0 hours and the reactortube effluent after 168 and 849 hours. Linear C₁₀-C₁₄ olefins wereconverted in a 94% yield to branched C₁₀-C₁₄ olefins after a 168 hrprocessing time. During the isomerization step, less than 3 weightpercent of material boiling below C₁₀ was generated from cracking sidereactions. The average number of alkyl branches on the C₁₀-C₁₄ olefinsin the product was determined to be 1.3 by ¹H NMR analysis. TABLE 41-Dodecene Stream Composition 0 Hr 168 Hr 849 Hr During IsomerizationReaction Wt. % Wt. % Wt. % <C₁₀ hydrocarbons 0.2 2.5 2.4 C₁₀-C₁₄hydrocarbons 99.6 97.2 97.4 >C₁₄ hydrocarbons 0.2 0.3 0.2 BranchedC₁₀-C₁₄ olefins 0.6 93.2 93.4 Linear C₁₀-C₁₄ olefins 99.0 2.8 2.9Paraffins 1.0 2.0 1.9

Example 3 Dehydrogenation of Dodecane with Minimal Isomerization

Dodecane was obtained from Aldrich Chemical Company and stored undernitrogen before being processed. The composition of dodecane, as assayedby gas chromatography, is tabulated in Table 5. TABLE 5 DodecaneComposition Wt. % Dodecane 99.3 <C₁₀ hydrocarbons <0.1 C₁₀, C₁₁, C₁₃ andC₁₄ hydrocarbons <0.6 >C₁₄ hydrocarbons <0.1 Other C₁₀-C₁₄ olefins <0.1

A paraffin dehydrogenation catalyst was prepared according to Example 1(catalyst A) of U.S. Pat. No. 4,430,517 to Imai et al., entitled“Dehydrogenation Process Using A Catalytic Composition”, which isincorporated by reference herein. The resulting catalyst included 0.8wt. % platinum, 0.5 wt. % tin, 2.7 wt. % tin, 2.7 wt. % potassium and1.3 wt. % chlorine on a gamma-alumina support. The atomic ratio ofpotassium to platinum for this catalyst was 16.8.

The dehydrogenation catalyst was prepared by dissolving substantiallypure aluminum pellets in a hydrochloric acid solution. An amount ofstannic chloride was added to the resulting solution to provide a finalcomposite containing 0.5 weight % tin and stirred to distribute the tincomponent evenly throughout the mixture. Hexamethylenetetramine wasadded to the resulting tin mixture and the resulting tin-amine mixturewas dropped into an oil bath in a manner to form spherical particleshaving an average particle diameter of about 1/16 inch. The spheres wereaged, washed with an ammoniacal solution, dried and calcined to form aspherical gamma-alumina carrier material. The resulting spherescontained about 0.5 weight % tin in the form of tin oxide. More detailsabout the method of preparing the alumina carrier material are disclosedin U.S. Pat. No. 2,620,314 to Hoesktra, entitled, “Spheroidal Alumina,”which is incorporated by reference herein.

The tin-alumina composite was contacted with a deionized solution ofchloroplatinic acid and hydrochloric acid (2 weight percent based onalumina weight) in a rotary drier for 15 minutes at room temperature.The amount of chloroplatinic acid used was the amount necessary toincorporate 0.8 weight percent platinum into the tin-alumina composite.The solution was then heated and purged with nitrogen to remove waterresulting in a platinum-chlorine-tin-alumina composite. The incorporatedchlorine was removed by heating the platinum-chlorine-tin-aluminacomposite to 550° C. and treating the composite with a 50/50 air/80° C.steam mixture at a gas hourly space velocity (GHSV) of 300 hr⁻¹. Aftertreatment with the air/steam mixture, the platinum-tin-alumina compositecontained less than 0.1 weight percent chlorine.

The platinum-tin-alumina composite was contacted with a deionized watersolution of potassium nitrate. The amount of potassium nitrate used wasthe amount necessary to incorporate 2.7 weight percent of potassium inthe platinum-tin-alumina composite. The water was removed from theplatinum-tin-potassium-alumina composite by heating the composite to100° C. under a purge of dry air (1000 hr⁻¹ GHSV) for 0.5 hour. Thetemperature was raised to 525° C. and the platinum-tin-potassium aluminacomposite was treated with a stream of hydrochloric acid (12 cc/hr, 0.9M HCl) and a stream of 50/50 air/80° C. steam mixture (300 hr⁻¹ GHSV) toincorporate chlorine into the platinum-tin-potassium-alumina composite.The platinum-tin-potassium-chlorine-alumina composite was dried at 525°C. under a purge of dry air (1000 hr⁻¹ GHSV). The resulting catalystspheres had an average particle diameter of 1/16 inch and were crushedand sized into 6-20 mesh particle before testing.

Stainless steel tubing, 1 inch OD, 0.6 inch ID and 26 inches long, wasused as an isomerization reactor. A thermowell extended 20 inches fromthe top of the stainless steel reactor tube. To load the reactor tube,the reactor tube was inverted and a piece of glass wool was transferreddown the wall of the reactor tube, over the thermowell and positioned atthe bottom of the reactor tube to serve as a plug for the reactor tube.Silicon carbide (20 mesh) was added to a depth of about 6 inches to thereactor tube. A second piece of glass wool was placed over the siliconcarbide. A mixture of 6.0 grams of platinum-tin on alumina catalystparticles (6-20 mesh) and 45 grams of fresh silicon carbide (60-80 mesh)was added to the reactor tube in two parts. The two-part additiondistributed the catalyst evenly in the reactor tube and resulted in acatalyst bed of about 10 inches in length. A third piece of glass woolwas added to the top of the catalyst in the reactor tube. Siliconcarbide (20 mesh) was layered onto the third piece of glass wool. Afourth piece of glass wool was positioned over the silicon carbide toserve as a plug for the bottom of the reactor tube. To monitor thetemperature of the reaction at various points in the reactor tube, amultipoint thermocouple was inserted into the thermowell of the reactortube. The temperature above, below and at three different places in thecatalyst bed was monitored. The reactor tube was inverted and installedin the furnace. The reactor tube was purged with nitrogen. The reactortube was heated to the operating temperature of 425° C. over a four-hourperiod under flowing nitrogen (250 standard liters per hour). Once thetemperature of 425° C. was obtained, the reactor tube was held at theoperating temperature for an additional two hours. The catalyst waspresulfided by flowing a 1% mixture of hydrogen sulfide gas in hydrogengas at 425° C. for five minutes through the reactor tube. After 5minutes, the hydrogen sulfide in hydrogen gas flow was switched to ahydrogen gas flow through the reactor tube.

After presulfiding the catalyst, the reactor tube was maintained at 425°C. for eight hours. After eight hours, the reactor tube pressure wasincrease to 25 psig with hydrogen gas. Dodecane was pumped through thereactor tube at a flow rate of 40 g/hr at a hydrogen flow rate of 125standard liters per hour. After four hours, the dodecane stream wasincreased to 80 g/hr. After obtaining a flow rate of 80 g/hr, thereactor tube temperature was raised to 460° C. The reactor tube wassampled every eight hours after obtaining the operating temperature of460° C.

After twenty-four hours the weight percent of dodecane was 11.4 weightpercent as depicted in Table 6. At a temperature of 479° C., theconversion of dodecane to olefins was 16 weight percent aftertwenty-four hours. Of the olefins, formed 84 weight percent were monoolefins, 4.1 weight percent were aromatic compounds and 7.5 weightpercent were di-olefins. Of the total amount of olefins formed, 6percent were branched, as determined by ¹H NMR analysis. TABLE 6 TestResults. Conversion (wt. %) after 24 hours on-stream at 460° C. 11.4Temperature required for 16 wt. % conversion 479° C. Selectivity to monoolefins at 16 wt. % conversion.  84 wt. % Selectivity to aromatics at 16wt. % conversion. 4.1 wt. % Selectivity to di-olefins at 16 wt. %conversion. 7.5 wt. % % Branched C₁₂ olefins in total C₁₂ olefins, (wt.%)   6

Example 4 Dehydrogenation—Isomerization of Dodecane

Dodecane was obtained from Aldrich Chemical Company and stored undernitrogen before being processed. The composition of dodecane, as assayedby gas chromatography, is tabulated in Table 5.

A dehydrogenation-isomerization catalyst was prepared in the followingmanner. Ammonium-ferrierite (645 grams) exhibiting a 5.4% loss onignition and exhibiting the following properties: molar silica toalumina ratio of 62:1, surface area of 369 square meters per gram(P/Po=0.03), soda content of 480 ppm and n-hexane sorption capacity of7.3 g per 100 g of ammonium-ferrierite was loaded into a Lancaster mixmuller. CATAPAL® D alumina (91 grams) exhibiting a loss on ignition of25.7% was added to the muller. During a five-minute mulling period, 152milliliters of deionized water was added to thealumina/ammonium-ferrierite mixture. Next, a mixture of 6.8 gramsglacial acetic acid, 7.0 grams of citric acid and 152 milliliters ofdeionized water was slowly added to the alumina/ammonium-ferrieritemixture in the muller to peptize the alumina. The resultingalumina/ammonium-ferrierite/acid mixture was mulled for 10 minutes. Overa period of 15 minutes, a mixture of 0.20 grams of tetraamine palladiumnitrate in 153 grams of deionized water was slowly added to mulledalumina/ammonium-ferrierite/acid mixture. The resulting mixtureexhibited a 90:10 ratio of zeolite to alumina and a loss on ignition of43.5%. The zeolite/alumina mixture was shaped by extruding the mixturethrough a stainless steel die plate ( 1/16″ holes) of a 2.25 inch Bonnotextruder.

Six grams of the resulting zeolite/alumina mixture was impregnated withan aqueous solution of sodium hexachloroplatinate [IV] hexahydrate toincorporate 0.8 wt. % platinum into the 1/16 inch extrudate. The moistzeolite/alumina platinum impregnated extrudate was dried at 125° C. for2 hours in flowing air. The temperature was raised to a maximumtemperature of 500° C. and the zeolite/alumina platinum impregnatedextrudate was calcined to yield a dehydrogenation-isomerizationcatalyst. The calcined catalyst was crushed and sized into 6-20 meshparticles before testing.

Dodecane was dehydrogenated and isomerized using the same reactor tubedesign as described in Example 3. A 16.1 weight percent conversion ofdodecane to olefins was observed after twenty-fours hours at 459° C. Astabulated in Table 7, of the olefins formed 86 weight percent were monoolefins, 1.2 weight percent were aromatic compounds and 6.8 weightpercent were di-olefins. Of the total amount of olefins formed, 86percent were branched, as determined by ¹H NMR analysis. TABLE 7 TestResults. Conversion (wt. %) after 24 hours on-stream at 460° C. 16.1Temperature required for 16 wt. % conversion 459° C. Selectivity to monoolefins at 16 wt. % conversion.  86 wt. % Selectivity to aromatics at 16wt. % conversion. 1.2 wt. % Selectivity to di-olefins at 16 wt. %conversion. 6.8 wt. % % Branched C₁₂ olefins in total C₁₂ olefins, (wt.%)  86

Example 5 Dehydrogenation-Isomerization Catalyst

A zeolite portion of a dehydrogenation-isomerization catalyst wasprepared as in Example 4. Six grams of the resulting zeolite/aluminamixture was impregnated with an aqueous solution of tetraamine palladiumnitrate to incorporate 0.8 wt. % palladium into the 1/16 inchextrudates.

The moist zeolite/alumina palladium impregnated extrudate was dried at125° C. for 2 hours in flowing air. The temperature was raised to amaximum temperature of 500° C. and the zeolite/alumina platinumimpregnated extrudate was calcined to yield adehydrogenation-isomerization catalyst. The calcined catalyst wascarefully crushed and sized into 6-20 mesh particles before testing.

Example 6 Dehydrogenation-Isomerization Catalyst

A dehydrogenation-isomerization catalyst was prepared according to themethod for catalyst D of U.S. Pat. No. 5,648,585 to Murray et al.,entitled, “Process For Isomerizing Linear Olefins To Isoolefins”, whichis incorporated by reference herein.

Ammonium-ferrierite having a molar silica to alumina ratio of 62:1, asurface area of 369 m2/g (P/Po=0.03), a soda content of 480 ppm wt and an-hexane sorption capacity of 7.3 grams per 100 grams of zeolite wasused. The catalyst components were mulled using a Lancaster mix muller.The mulled catalyst material was extruded using a Bonnot pin barrelextruder. The binder utilized was CATAPAL® D alumina from Sasol.METHOCEL® F4M, hydroxypropyl methylcellulose, from The Dow ChemicalCompany was used as an extrusion aid.

The Lancaster mix muller was loaded with 632 grams of ammoniumferrierite (LOI of 3.4%) and 92 grams of CATAPAL®D alumina (LOI of26.2%). The alumina was blended with the ferrierite for five minutesduring which time 156 milliliters of de-ionized water was added. Amixture of 6.8 grams of glacial acetic acid and 156 milliliters ofde-ionized water were added slowly to the muller in order to peptize thealumina. The mixture was mix-mulled for 10 minutes. Tetraamine platinumnitrate and Tetraamine palladium nitrate were added to the mix-muller inorder to produce a catalyst that contained 0.25 wt. % palladium and 0.55wt. % platinum. Ten grams of METHOCEL® F4M hydroxypropyl methylcellulosewas added and the zeolite/alumina was mulled for 15 additional minutes.The extrudate was transferred to a Bonnot pin barrel extruder andextruded using a stainless steel die plate with 1/16 inch holes. Theextrudate was dried at 120° C. for 16 hours and then calcined in air at500° C. for 2 hours. The calcined catalyst was carefully crushed andsized into 6-20 mesh particles before testing.

Example 7 Dimerization of 1-Hexene

A dimerization catalyst for the dimerization of a C₆ olefin stream wasprepared by the method for Example 1 in U.S. Pat. No. 5,169,824 to Salehet al., entitled, “Catalyst Comprising Amorphous NiO On Silica/AluminaSupport”, which is incorporated by reference herein.

An aluminosilicate cogel (100 gram, 87% by weight SiO₂-13% by weightAl₂O₃) was dispersed in distilled water (2000 mL). Aluminosilicate cogelmay be obtained from Ineos Silicas, Netherlands BV, as Synclist-13.Nitric acid (65%) was added to the aluminosilicate/water dispersion withstirring until a pH of 2.7 was obtained. The resulting acidic mixturewas filtered and the aluminosilicate solid washed with distilled wateruntil the filtrate exhibited a pH of 5.7. The recovered aluminosilicatesolid was dispersed again in distilled water and nitric acid (65%) wasadded until a pH of 2.7 was obtained. The resulting acidic mixture wasfiltered and the resulting aluminosilicate solid was washed withdistilled water until the filtrate exhibited a pH of 5.7. The recoveredaluminosilicate solid was dried for 16 hours at 110° C. in an airatmosphere and thereafter calcined at 500° C. for 16 hours under an airatmosphere.

Ni(NO₃)₂.0.6H₂O (67.38 gram) was dissolved in distilled water (700 mL)and heated to a temperature of 32° C. to result in a solution having apH of 5.7. The aluminosilicate solid (35 gram) was added over time tothe nickel solution resulting in a nickel/aluminosilicate slurry. The pHof the nickel/aluminosilicate slurry was approximately 3.9. Thenickel/aluminosilicate slurry was neutralized by adding a solution of(NH₄)₂CO₃ (33.69 gram) in distilled water (200 mL) drop wise over 30minutes until the pH of the slurry was approximately 6.9. The neutralslurry was stirred for 30 minutes at 32° C. and then filtered to obtaina solid. The recovered solid was slurried twice with water to theoriginal volume of the nickel/aluminosilicate slurry, stirred for 5minutes and then filtered to obtain a solid. The resulting solid wasdried at 110° C. for 16 hours in an air atmosphere. Calcination of thesolid was performed by heating the solid under an air atmosphere atincreasing temperatures. Initially, the solid was heated to 232° C. for1 hour. The temperature was raised to 371° C. and the solid heated for 2hours. After 2 hours, the temperature was raised to 592° C. and thesolid was heated for 16 hours. The resulting NiO catalyst dispersed onan aluminosilicate support was crushed and carefully sized to slightlygreater than 60 mesh before testing.

A 15 mL reactor tube of an autoclave unit was charged with the NiOcatalyst (0.335 grams), 1-hexene (3.35 grams), and a gas chromatographystandard (0.67 grams linear tetradecane). Autoclave units of the type“Endeavour” from Argonaut Technologies, United Kingdom, were used toperform the dimerization experiments. The gas cap of the reactor tubewas flushed with nitrogen and the reactor tube was heated to 160° C.Once the reaction temperature of 160° C. was obtained, the reactiontemperature was maintained for 10 hours and then cooled to roomtemperature. The reaction mixture was filtered to remove the NiOcatalyst and the filtrate was analysed by gas chromatography. Thedimerization results are tabulated in Table 8. TABLE 8 Test Results.Conversion of 1-hexene (%) 59 C₁₂ olefin dimer in reaction mixture (wt%) 22 Branched C₁₂ olefins in total C₁₂ olefins (wt. %) 77

Example 8 Dimerization of Diluted 1-Hexene

A 15 mL reactor tube of the autoclave unit was charged with the NiOcatalyst (0.335 grams) prepared according to the method for Example 7,1-hexene (1.675 grams), hexane (1.675 grams) and a gas chromatographystandard (0.67 grams linear tetradecane). The gas cap of the reactortube was flushed with nitrogen and the reactor tube was heated to 160°C. Once the reaction temperature of 160° C. was obtained, the reactiontemperature was maintained for eight hours and then cooled to roomtemperature. The reaction mixture was filtered to remove the NiOcatalyst and the filtrate was analyzed by gas chromatography. Thedimerization results are tabulated in Table 9. TABLE 9 Test Results.Conversion of 1-hexene (wt. %) 54 C₁₂ olefin dimer in reaction mixture(wt %)  8 % Branched C₁₂ olefins in total C₁₂ olefins 82

In this patent, certain U.S. patents and U.S. patent applications havebeen incorporated by reference. The text of such U.S. patents and U.S.patent applications is, however, only incorporated by reference to theextent that no conflict exists between such text and the otherstatements and drawings set forth herein. In the event of such conflict,then any such conflicting text in such incorporated by reference U.S.patents and U.S. patent applications is specifically not incorporated byreference in this patent.

Further modifications and alternative embodiments of various aspects ofthe invention will be apparent to those skilled in the art in view ofthis description. Accordingly, this description is to be construed asillustrative only and is for the purpose of teaching those skilled inthe art the general manner of carrying out the invention. It is to beunderstood that the forms of the invention shown and described hereinare to be taken as examples of embodiments. Elements and materials maybe substituted for those illustrated and described herein, parts andprocesses may be reversed, and certain features of the invention may beutilized independently, all as would be apparent to one skilled in theart after having the benefit of this description of the invention.Changes may be made in the elements described herein without departingfrom the spirit and scope of the invention as described in the followingclaims.

1-204. (canceled)
 205. A method for the production of aliphatic alcohols, comprising: introducing a first hydrocarbon stream comprising olefins and paraffins into an isomerization unit, wherein the isomerization unit is configured to isomerize at least a portion of linear olefins in the first hydrocarbon stream to branched olefins, and wherein at least a portion of the unreacted components of the first hydrocarbon stream and at least a portion of the produced branched olefins form a second hydrocarbon stream; introducing at least a portion of the second hydrocarbon stream into a hydroformylation unit, wherein the hydroformylation unit is configured to hydroformylate at least a portion of the olefins in the second hydrocarbon stream to produce aliphatic alcohols, and wherein at least a portion of the produced aliphatic alcohols comprises a branched alkyl group, and wherein at least a portion of the unreacted components of the second hydrocarbon stream, and at least a portion of the produced aliphatic alcohols form a hydroformylation reaction stream; separating at least a portion of the hydroformylation reaction stream to produce an aliphatic alcohol product stream and a paraffins and unreacted olefins stream; and introducing at least a portion of the paraffins and unreacted olefins stream into a dehydrogenation unit, wherein the dehydrogenation unit is configured to dehydrogenate at least a portion of paraffins in the paraffins and unreacted olefins stream to produce olefins, and wherein at least a portion of the produced olefins exits the dehydrogenation unit to form an olefinic hydrocarbon stream; and introducing at least a portion of the olefinic hydrocarbon stream into the isomerization unit.
 206. The method of claim 205, wherein the first hydrocarbon stream is produced from an olefin oligomerization process.
 207. The method of claim 205, wherein the first hydrocarbon stream is produced from a Fischer-Tropsch process.
 208. The method of claim 205, wherein the first hydrocarbon stream comprises olefins and paraffins having a carbon number from 10 to
 13. 209. The method of claim 205, wherein the first hydrocarbon stream comprises olefins and paraffins having a carbon number from 10 to
 17. 210. The method of claim 205, wherein the isomerization unit is operated at a reaction temperature between about 200° C. and about 500° C.
 211. The method of claim 205, wherein the isomerization unit is operated at a reaction pressure between about 0.1 atmosphere and about 20 atmospheres.
 212. The method of claim 205, wherein at least a portion of the branched olefins comprise an average number of branches per total olefin molecules of at least 0.7.
 213. The method of claim 205, wherein at least a portion of the branched olefins comprise methyl and ethyl branches.
 214. The method of claim 205, wherein at least a portion of the branched olefins comprise an average number of branches per total olefin molecules of less than 2.5.
 215. The method of claim 205, wherein at least a portion of the branched olefins comprise an average number of branches per total olefin molecules of between about 0.7 and about 2.2.
 216. The method of claim 205, wherein at least a portion of the branched olefins comprise an average number of branches per total olefin molecules of between about 1.0 and about 2.2.
 217. The method of claim 205, wherein greater than 50 percent of the branched groups on the branched olefins are methyl groups.
 218. The method of claim 205, wherein less than 30 percent of the branched groups on the branched olefins are ethyl groups.
 219. The method of claim 205, wherein less than 10 percent of the branched groups on the branched olefins are groups other than methyl or ethyl groups.
 220. The method of claim 205, wherein the branched olefins have less than 0.5 percent aliphatic quaternary carbon atoms.
 221. The method of claim 205, wherein the branched olefins have less than 0.3 percent aliphatic quaternary carbon atoms.
 222. The method of claim 205, wherein the hydroformylation unit is configured to produce greater than 50 percent of aliphatic alcohols.
 223. The method of claim 205, wherein the hydroformylation unit is configured to produce greater than 95 percent of aliphatic alcohols.
 224. The method of claim 205, wherein the hydroformylation unit is operated at a reaction temperature from about 100° C. to about 300° C.
 225. The method of claim 205, wherein the branched alkyl groups of the aliphatic alcohols comprise about 0.5 percent or less aliphatic quaternary carbon atoms, and an average number of branches per alkyl group of at least 0.7, the branches comprising methyl and ethyl branches.
 226. The method of claim 205, further comprising adjusting a ratio of olefins to paraffins introduced into the isomerization unit by adding at least a portion of a paraffinic hydrocarbon stream into the isomerization unit.
 227. The method of claim 205, further comprising: adjusting a ratio of olefins to paraffins introduced into the isomerization unit by combining a paraffinic hydrocarbon stream with at least a portion of the first hydrocarbon stream upstream of the isomerization unit to form a combined stream; and introducing the combined stream into the isomerization unit.
 228. The method of claim 205, further comprising adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by adding at least a portion of a third hydrocarbon stream into the hydroformylation unit.
 229. The method of claim 205, further comprising adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by adding at least a portion of a third hydrocarbon stream into the hydroformylation unit, wherein the third hydrocarbon stream comprises greater than 80 percent olefins by weight.
 230. The method of claim 205, further comprising: adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream; and introducing the combined stream into the hydroformylation unit.
 231. The method of claim 205, further comprising: adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein the third hydrocarbon stream comprises greater than 80 percent olefins by weight; and introducing the combined stream into the hydroformylation unit.
 232. The method of claim 205, further comprising: adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein the third hydrocarbon stream comprises linear olefins; and introducing the combined stream into the hydroformylation unit.
 233. The method of claim 250, further comprising: adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein at least a portion of the second hydrocarbon stream comprises branched olefins; and introducing the combined stream into the hydroformylation unit.
 234. The method of claim 205, further comprising: adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein at least a portion of the third hydrocarbon stream comprises linear olefins and at least a portion of the second hydrocarbon stream comprises branched olefins; and introducing the combined stream into the hydroformylation unit.
 235. The method of claim 205, further comprising: adjusting a ratio of olefins to paraffins introduced into the isomerization unit by combining at least a portion of a paraffinic hydrocarbon stream with at least a portion of the first hydrocarbon stream upstream of the isomerization unit to form a combined stream; introducing the combined stream into the isomerization unit; adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream; and introducing the combined stream into the hydroformylation unit.
 236. The method of claim 205, wherein the dehydrogenation unit is operated at a temperature between about 300° C. and about 700° C.
 237. The method of claim 205, wherein the dehydrogenation unit is operated at a pressure between about 0.01 atmosphere and about 25 atmospheres.
 238. The method of claim 205, further comprising introducing at least a portion of the aliphatic alcohol product stream into a sulfation unit, wherein the sulfation unit is configured to sulfate at least a portion of the aliphatic alcohols in the aliphatic alcohol product stream to produce aliphatic sulfates, and wherein at least a portion of the aliphatic sulfates produced comprises branched aliphatic sulfates.
 239. The method of claim 205, further comprising introducing at least a portion of the aliphatic alcohol product stream into an oxyalkylation unit, wherein the oxyalkylation unit is configured to oxyalkylate at least a portion of the aliphatic alcohols in the aliphatic alcohol product stream to produce oxyalkyl alcohols, wherein at least a portion of the oxyalkyl alcohols produced comprises branched oxyalkyl alcohols. 240-270. (canceled) 